A practical, highly flexible and eco-friendly method has been developed for the synthesis of allyl thiosulfonates using Morita–Baylis–Hillman (MBH) allyl bromides and sodium arylthiosulfonates, which were readily assembled without any reagent/catalyst. Moreover, the allyl thiosulfonates were successfully transformed into a set of two synthetically viable diallyl disulfanes and unsymmetrical allyl disulfanes in the presence of Cs₂CO₃. The present protocols are operationally simple and convenient to generate a wide range of functionalized allyl thiosulfonates and allyl disulfanes in good to excellent yields.