Sunrise's anime series Valvrave the Liberator features several fictional characters designed by manga artist Katsura Hoshino. Set in the futuristic 71st Year of the True Calendar, the series follows Haruto Tokishima a high school student from the faction of JIOR who pilots an advanced mecha known as Valvrave 01 to defeat the hostile Dorssian forces invading his home. In order to defend themselves from the enemies who wish the Valvrave, Haruto's childhood friend Shoko Sashinami convinces her school mates to become an independent nation, the New JIOR. Across the fights against the Dorssia forces, Haruto gains new allies including the Dorssia agent L-elf who wishes to bring a revolution to his country, former idol Saki Rukino who becomes the Valvrave 04 pilot, school mates Kyūma Inuzuka and Raizo Yamada who wish to avenge their comrades using the Valvraves as well as the isolated girl Akira Renbokoji who becomes the final Valvrave pilot to protect Shoko.

New JIOR The is a nation composed of students from the former JIOR who are forced to become independent as the forces of Dorssia and ARUS are chasing them to obtain the mecha Valvrave. As the series progresses, it is revealed all the students were experimented from an early age to operate the machines and become immortals.

Haruto Tokishima is a high school student who always tries to avoid conflict, claiming that fighting is not the best way to deal with issues. He is thus displayed as an extremely kind hearted individual. During the Dorssian invasion, his friend Shoko presumably gets struck by a Dorssian mech, urging him to seek revenge with the mysterious humanoid weapon called the Valvrave. After learning that Shoko survived, he chooses not to declare his feelings for her, deeming himself unfit to be with her as a result of the Valvrave's effect on him. The Valvrave gives him a berserker state where he tries to bite other people and feed on their "Runes", their DNA. This curse also gives him special regenerative capabilities that allow him to survive wounds that could be fatal to ordinary humans, as well as the ability to transfer his consciousness into another person's body, by biting a person's bare skin, leaving his own body lying unconscious until he returns to it. The more Haruto pilots the Valvrave, the more memories he loses with the loss of all leading him to his death. Haruto's secret of his nature causes Shoko to sell him to Arus to negotiate for the lives of New JIOR students. Nevertheless, Haruto realizes he still cherishes mankind and agrees to work with L-elf to build a world where everyone including humans and Magius can live in peace. In revealing the truth behind the Magius, Haruto uses his last Runes in order to defeat Dorssia commander Cain Dressel. After L-elf admits that Haruto is his friend, he lightly taps L-elf's face, smiling to him as he dies. He is voiced by Ryōta Ōsaka in Japanese and by Johnny Yong Bosch in English.

L-elf , whose real name is Michael, is a secret agent of the Dorssian military. He is an excellent strategist and his innate ability to calculate possibilities has been referenced to be almost prophetic in nature. L-elf is known in ARUS as the "One Man Army" for having killed almost 5000 soldiers single-handedly. He always carries around a photo of the Dorssian Princess Lieselotte who had saved his life when he was younger, and has feelings for her. During Dorssia's invasion to Jior he tries to kill Haruto but the Valvrave's curse causes Haruto to possess his body. He is considered a traitor by Dorssia due to the actions Haruto commits while in control of his body, and is effectively stranded on Module 77. While claiming that he intends to bring about a revolution in Dorssia, he tries to convince Haruto to become his ally. Haruto accepts his offer and L-elf starts guiding the forces of New JIOR. When going to the Earth, L-elf tries to save Lieselotte from Dorssia but she dies in the fight against them. After learning Lieselotte was a Magius, L-elf agrees with Haruto to build a unified world where everyone including humans and Magius can live in peace. In the final episode, he admits that Haruto is his friend just before the latter dies, he is later seen in the epilogue during Satomi and Takahi's wedding party wearing an imperial cloth. He is voiced by Ryōhei Kimura in Japanese and by Robbie Daymond in English.

Shoko Sashinami is the daughter of the prime minister of JIOR, and is Haruto's childhood friend and crush. She is extremely kindhearted and loyal to her friends. She seems to reciprocate Haruto's feelings for her, but his confession to her is interrupted by the Dorssian invasion, and her presumed death is the reason for Haruto to pilot the Valvrave. With the rest of the country under Dorssia's control and following ARUS's betrayal, she convinces the other students to establish the Sakimori Academy's module as an independent state called New JIOR, using the Valvrave as leverage against both superpowers. She is elected as the first Prime Minister of New JIOR. After she finds out Haruto's secret, she sells L-Elf and him to ARUS to negotiate for their lives, as she no longer trusts him. However, she quickly learns from Pino that the reason Haruto turned into a Kamitsuki was to avenge her presumed death back in Episode 1, bursting into tears upon the revelation. She deeply grieves over Haruto's death, but still tries to look strong for the sake of her citizens. In the epilogue, she eventually becomes an immortal and replaces Haruto as the new pilot of Valvrave 01, and has had a 'Memorial Core' built, with statues of those who died to create their new home. She is voiced by Asami Seto in Japanese and by Michelle Ruff in English.

Saki Rukino is a popular idol who has grown aloof due to her career being on hold, due to her being cold and that she hates dealing with other people. She develops feelings for Haruto but is jealous of his friendship with Shoko. After discovering the Valvrave hangar beneath Sakimori Academy, she excitedly pilots the Valvrave Four (coded VVVIV), to which she names "Carmilla", after being injected with the same substance as Haruto. 200 years in the future Saki is still a Valvrave pilot fighting an unknown enemy and remembers her promise with Haruto to not give up no matter what. During this time she is often seen talking with the young Prince, telling him stories about the Magius War. She is also the protagonist of the manga Ryūsei no Valkyrie which explores her role in the series as well as her backstory. She is voiced by Haruka Tomatsu in Japanese and by Cherami Leigh in English.

Kyūma Inuzuka is a high school senior and a very dependable upperclassman for Haruto and his classmates. He is constantly thinking about ways to make money and hopes to become a very rich man in the future. Kyuma is one of Haruto's friends at school and one of the first to witness Haruto's power. After learning of Aina's death, he becomes a Valvrave pilot in order to avenge her. Later on, he dies by sacrificing himself to protect the escaping students during the massacre, even though they called him and his comrades monsters and tried to kill them. He is voiced by Yūki Ono in Japanese and by J. Michael Tatum in English.

Aina Sakurai is a very caring but extremely shy freshman at Sakimori Academy. She is able to connect with Saki, despite the latter normally isolating herself from the other students. Aina is another friend of Haruto's and one of the first to learn about his power. She is killed in the cross fire between Q-vier and L-elf, while hiding in the Valvrave hangar. She is voiced by Ai Kayano in Japanese and by Alexis Tipton in English.

Marie Nobi is Shoko's best friend. Contrary to her childish appearance, Marie is very emotionally mature and is never afraid of letting others know her opinions. She suffers from amnesia and has no recall of any memories beyond two years in the past. Her amnesia is the direct result of the Pino AI consuming the Runes of her memories during the early stages of Project VVV where she had been used as a test pilot for the Valvrave I. Marie's Runes are capable of greatly amplifying the Valvrave I's abilities. She eventually dies after using too much Runes when using Valvrave I during a battle. She is voiced by Misato Fukuen in Japanese and by Laura Bailey in English.

Yusuke Otamaya is the leader of the Boys' Cultural Club. He is extremely knowledgeable about the mechanics of machines and physics making others consider him a bit of a nerd. He and Raizo work together to fix the climate controls in Module 77. He is voiced by Hiroyuki Yoshino in Japanese and by Spike Spencer in English.

Raizo Yamada is the academy delinquent. He is nicknamed by the gang of misfits that he leads. He has a short temper, but cares about his friends. He helps Yusuke fix the climate controls in Module 77. He becomes a Valvrave pilot in order to avenge his friend. During season 2, Yamada works with Haruto, Akira, Saki and L-elf to expose the nature of the Magius. Yamada is killed protecting Akira in a one-on-one duel with Dorssia soldier Q-vier. He is voiced by Yūichi Nakamura in Japanese and by Keith Silverstein in English.

Satomi Renbokoji is the president of the student council of Sakimori Academy and brother of Akira. He demonstrates an elite disposition, but is usually helpless in crisis situations. He was pressured by his parents to pass an exam to get into one of the best national schools. When Akira was discovered to have hacked into the exam database and later suffered extensive bullying because of it, he distanced himself from her. Later in life, he tries to atone for this by being over-protective of Akira. He marries Takahi, as seen in the epilogue. He was believed to have appeared in the futuristic scenario, but this was later revealed to be his descendant. He is voiced by Daisuke Namikawa in Japanese and by Steve Cannon in English.

Takahi Ninomiya is a senior and the leader of the Girls' Sports Club at Sakimori Academy. She is very proud of being named Miss Sakimori for the last 2 school years. She can be an overbearing rich-girl at times. She is married to Satomi, as seen in the epilogue. She is voiced by Minako Kotobuki in Japanese and by Kari Wahlgren in English.

Akira Renbokoji is a shy but skilled hacker that operates several computers concealed by cardboard boxes in a hidden area in the academy and is essentially a hikikomori. In the past she was bullied in middle school after she was caught hacking the computer systems for the prestigious academy that her brother, Satomi took the entrance exam for so that he could be admitted. This led to her current lifestyle and fearing the outside world. She is the one that posts the video of Haruto initially piloting the Valvrave onto the WIRED Network. After overcoming her past fears and embracing her new friendship with Shoko, she becomes the pilot of Unit 6. In the epilogue, she is seen talking to the Prince and Saki. She is voiced by Aoi Yūki in Japanese and by Cristina Vee in English.

Takumi Kibukawa is a physics instructor at Sakimori Academy, but because of his aloof attitude towards everything and extremely casual tone, many find it difficult to see him as a member of the faculty. He seems to know one of the scientists who had worked on the Valvrave program. He later reveals that he and the rest of the staff at the academy (with the exception of Rion Nanami) and the adults of Module 77 were JIOR soldiers. He is voiced by Wataru Hatano in Japanese and by Doug Erholtz in English.

Rion Nanami is a teacher at Sakimori Academy. She is bit of an air-head at times and is the only member of the faculty not involved with the Valvrave project. Her sweet personality and attractive physical features makes her popular among the male students. She is voiced by Yui Horie in Japanese and by Melissa Fahn in English.

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