A photocatalytic decyanative C(sp 3 )−H pyridination of dihydroquinoxalin-2-ones with 4-cyanopyridines was developed by utilizing 4CzIPN as the photocatalyst. Mechanism studies show that this organophotocatalytic direct C(sp 3 )−H pyridination undergoes a radical−radical cross-coupling pathway promoted by consecutive photoinduced electron transfer.