Photoredox-catalyzed difunctionalizations of alkenes with O-acyl hydroxylamine derivatives are described. The solvent tunes the outcome of these reactions. Diamidation and oxidative amidation of alkenes can be achieved in CH3CN and DMSO, respectively. A variety of 1,2-diamidates and α-amino ketones bearing many functional groups are prepared using Ir(ppy)3 as the photocatalyst under visible light irradiation.