Pompilio is a surname. Notable people with the surname include:

Afrânio Pompílio Gastos do Amaral (1894–1982), Brazilian herpetologist Arsénio Pompílio Pompeu de Carpo (1792–1869), Portuguese slave trader, freemason, poet and journalist Elvis Pompilio (born 1961), Belgian fashion designer Luca Pompilio (born 1992), Italian footballer Numa Pompilio Llona (1832–1907), Ecuadorian poet, journalist, educator, diplomat, and philosopher Pedro Pompilio (1949–2008), Argentine businessman and football chairman