A simple and efficient method for the synthesis of unsymmetrical disulfides is reported. Using sodium sulfites and 2mercaptobenzo heterocyclic compounds as starting materials, the unsymmetrical sulfur−sulfur bonds could be quickly constructed in the PPh 3 /I 2 reaction system under transition−metal-free conditions. This protocol has the advantages of mild reaction conditions, easily available starting materials, and wide substrate scope, showing potential synthetic value for the synthesis of a diversity of biologically or pharmaceutically active compounds.