Herein, we provide a novel method for the synthesis of 1,3-dibenzenesulfonylpolysulfane (DBSPS), which further reacts with boronic acids to afford thiosulfonates. Commercially available boron compounds greatly expanded the range of thiosulfonates. Experimental and theoretical mechanistic investigations suggested that DBSPS could provide both thiosulfone fragments and dithiosulfone fragments, but the generated aryl dithiosulfonates were unstable and decomposed into thiosulfonates.