Supported hydrogen peroxide on polyvinylpolypyrrolidone (PVPP– –H2O2), silica sulfuric acid (SiO2–OSO3H) and catalytic amounts of potassium iodide (KI) was developed as a heterogeneous medium for the rapid oxidative coupling of thiols into symmetrical homodisulfides. This oxidizing system proceeds under extremely mild conditions and gives no other oxidized side products.