Photoinduced Nickel‐Catalyzed Carbon–Heteroatom Coupling**

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 NiI /NiIII cycle via the generation of active NiI complexes that appear from homolysis of NiII -I rather than NiII -aryl bond was tentatively proposed.