The structure of the novel photoactive nickel species was simulated by density functional theory (DFT)/time-dependent density functional theory (TD-DFT) calculations. The application of the simplified photoactive nickel catalyst was demonstrated in a photoinduced nickel-catalyzed three-component arylsulfonation of 1,6-enynes. This reaction was autopromoted and proceeded in the absence of an additional photocatalyst. This methodology exhibited mild conditions, a broad substrate scope, and high efficiency.