A visible-light-mediated radical allylation of primary amine-derived Katritzky salts with allylic sulfones via C(sp³)–N bond activation is reported, furnishing the corresponding alkenes in satisfactory yields. This mild protocol provides an efficient strategy for site-specific C(sp³)–C(sp³) bond formation using abundant feedstock primary amines, particularly α-amino acids as alkyl radical precursors. This photocatalytic reaction demonstrates a broad substrate scope and good functional group tolerance.