Organosulfurs are important commodity chemicals and indispensable synthetic intermediates in modern chemistry that were traditionally synthesized using metal catalysts, oxidants or strong bases, which caused numerous environmental pollution issues. The divergent synthesis of these scaffolds via a single catalysis under catalyst and oxidant free conditions is a fantastic idea to overcome these drawbacks. Here, we report a safe, practical and eco-friendly electrochemical methodology for the controllable dechloro-coupling of 1,2-dichloroethane (DCE) with thiols, providing value-added β-chloroethylsulfurs, which serve as versatile building blocks in the efficient late-stage conversion to bioactive molecules. The mildness and practicality of this protocol was further demonstrated by the total synthesis of anti-gout drug sulfinpyrazone in a 32% total yield over three steps.