Different from the traditional two-electron oxidative addition-transmetalation-reductive elimination coupling strategy, visible light has been successfully integrated for the first time into transition metal-catalyzed coupling reaction of propargylic alcohol derivatives highly selectively forming allenenitriles: specifically speaking, visible light-mediated Cu-catalyzed cyanation of propargylic oxalates has been realized for the general, efficient, and exclusive syntheses of di-, tri-, and tetra-substituted allenenitriles bearing various synthetically versatile functional groups. Fluorescence quenching experiments combined with cyclic voltammetric measurements have proven that the current reaction proceeds via visible light-induced redox-neutral reductive quenching radical mechanism, which is a completely different approach as compared to the traditional transition metal-catalyzed two-electron oxidative addition processes. (Accepted by Nat. Commun.)