Herein, a heterogeneous carbonyl alkylative amination reaction that proceeds by photoredox catalysis has been developed. The use of nano titanium dioxide (TiO2, 25 nm) as photocatalyst allows efficient synthesis of diverse amines in good to excellent yields. Mechanistic studies reveal a single‐electron‐transfer mechanism involving the photoexcitation of TiO2 to generate alkyl radicals from carboxylic acids decarboxylation. This protocol highlights the utility of using heterogeneous semiconductor photocatalysts to promote a practical and general synthesis of complex amines from readily available feedstocks.