We reported the visible-light-mediated photoredox-catalyzed oxidative radical-polar crossover and 1,5-hydrogen atom transfer combined site-selective remote C(sp3)-N cross-coupling alkylamination of alkenes. Various anilines and hydroxamides (1,5-hydrogen atom transfer reagents) could be tolerated. The mechanistic studies indicated the radical nature of the reaction and the indispensability of light and photocatalyst. Stern-Volmer fluorescence quenching and cyclic voltammetry experiments have been used to outline the proposed reaction pathway.