An efficient enantioselective addition of alkyl radicals, oxidatively generated from organotrifluor-oborates, to acceptor-substituted alkenes is catalyzed by a bis-cyclometalated rhodium catalyst (4 mol %) under photoredox conditions. The practical method provides yields up to 97% with excellent enantioselectivities up to 99% ee and can be classified as a redox neutral, electron transfer-catalyzed reaction.