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
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