A visible-light organophotoredox-catalyzed sulfurization of alkenes and alkynes with aromatic and heteroaromatic thiols using eco-friendly air (O2) as the sole oxidant has been demonstrated. The established method delivers a novel, benign, and metal-free strategy for the difunctionalization of alkenes and alkynes using organophotoredox catalyst Eosin Y. The selective and controlled synthetic approach shows good substrate generality to afford sulfoxides, β-hydroxysulfoxides, and β-keto sulfides in high yield and excellent regioselectivity.