Napoléon Rioux (February 13, 1837 – September 15, 1899) was a seigneur, merchant and political figure in Quebec.
He represented Témiscouata in the Legislative Assembly of Quebec from 1892 to 1897 as a Conservative.
He was born in Trois-Pistoles, Lower Canada, the son of Jean-Baptiste Rioux and Marcelline Chamberland, and was educated there.
Rioux founded the local Saint-Jean-Baptiste Society in 1876 and also served as its president.
Rioux was defeated by Félix-Alonzo Talbot when he ran for reelection in 1897.