The visible-light-promoted catalyst-free condition has been demonstrated for self-and cross-coupling reactions of thiols in an ambient atmosphere. Further, synthesis of β-hydroxysulfides is accomplished under very mild conditions involving the formation of an electron donor−acceptor (EDA) complex between a disulfide and an alkene. However, the direct reaction of thiol with alkene via the formation of a thiol−oxygen co-oxidation (TOCO) complex failed to produce the desired compounds in high yields. The protocol was successful with several aryl and alkyl thiols for the formation of disulfides. However, the formation of β-hydroxysulfides required an aromatic unit on the disulfide fragment, which supports the formation of the EDA complex during the course of the reaction. The approaches presented in this paper for the coupling reaction of thiols and the synthesis of βhydroxysulfides are unique and do not require toxic organic or metal catalysts.