A nitrogen-centered radical-mediated carbon–carbon bond cleavage strategy is described to synthesize functionalized 3-acylcoumarins. The strategy is enabled by the visible-light-induced acylation/cyclization of alkynoates with various acyl oxime compounds in acetonitrile. The difunctionalization of carbon–carbon triple bonds precedes the generation of iminyl radicals, which is followed by the formation of acyl radicals. The acyl radicals then attack the carbon–carbon triple bonds, followed by 5-exo-trig cyclization and 1,2-ester migration. This strategy has wide substrate adaptability and good substituent tolerance.