Abstract: | A visible light accelerated C–H functionalization reaction in palladium‐catalyzed arylation of vinyl arenes with diaryliodonium salts is reported in the absence of additional photosensitizer. The kinetic isotope effect (kH/kD) was changed from 3.6 (under darkness) to 1.1 when irradiated by visible light, which indicated that the C–H functionalization step was the rate determining step under darkness and significantly accelerated by the irradiation of visible light. Finally the synthesis of ortho tetra‐substituted vinylarene atropisomers with high enantiospecificity was realized via this protocol. |