Herein, visible-light-induced metal-free three-component amidoheteroarylation of alkenes with quinoxalin-2(1H)-ones and N-sulfonylaminopyridinium salts is developed. This protocol involves a radical relay process in which the N-centered radicals undergo chemoselective addition to alkenes to form an alkyl radical that selectively combines with heteroarenes, leading to the formation of C−C and C−N bonds in one step under mild reaction conditions. The involved high efficiency and selectivity, wide substrate scope, and excellent functional-group compatibility demonstrate the practicability of the developed protocol.