Herein, we report a visible light-induced photocatalytic protocol for the thiolation and pyridylation of styenes using a thiolate-based EDA complex as a bifunctional reagent. The reaction occurrs under mild conditions free of a photocatalyst, metal or external redox agent, possessing a broad substrate scope. The protocol can be practiced on the gram-scale, and late-stage functionalization of natural product- and drug-derived complex molecules is also possible.