A photocatalytic process was devised to synthesize monofluoroalkenes via defluorinative functionalization of allylic difluorides. N-Alkylanilines are used as precursors to α-aminoalkyl radicals, which undergo regioselective addition to allylic difluorides, and subsequent SET and fluoride elimination produce monofluoroalkenes. C–C bond formation on the aniline is site-selective for the least substituted carbon α to nitrogen.