Napoleão is a Portuguese surname. Notable people with the surname include:
Alfredo Napoleão (1852–1917), Portuguese pianist and composer Annibal Napoleão (1845 or 1846–1880), Portuguese pianist and composer Arthur Napoleão dos Santos (1843–1925), Portuguese composer, pianist, instrument dealer and music publisher Sérgio Manuel Napoleão Ferreira (1946–2006), Portuguese–Cape Verdean writer and filmmaker Pedro Luiz Napoleão Chernoviz (1812–1882), physician, scientific writer and publisher