Photoinduced Nickel‐Catalyzed Carbon–Heteroatom Coupling**

Abstract Herein, we report visible light‐promoted single nickel catalysis for diverse carbon–heteroatom couplings under mild conditions. This mild, general, and robust method to couple diverse nitrogen, oxygen, and sulfur nucleophiles with aryl(heteroaryl)/alkenyl iodides/bromides exhibits a wide functional group tolerance and is applicable to late‐stage modification of pharmaceuticals and natural products. On the base of preliminary mechanistic studies, a Ni I /Ni III cycle via the generation of active Ni I complexes that appear from homolysis of Ni II −I rather than Ni II −aryl bond was tentatively proposed.