The direct introduction of sp3 carbon fragments at the β position of α,β-unsaturated aldehydes is greatly complicated by competing 1,2-addition manifolds. Previous catalytic enantioselective conjugate addition methods, based on the use of organometallic reagents or ground-state iminium ion activation, could not provide general and efficient solutions. We report herein that, by turning them into strong oxidants, visible light excitation of chiral iminium ions triggers a stereocontrolled radical pathway that exclusively affords highly enantioenriched β-substituted aldehydes bearing a variety of alkyl fragments.