Organosulfur compounds are widely used in medicinal and biochemistry, organic synthesis and material science. 1 Thus, the development of efficient method for the construction of C-S bond and the installation of sulfurcontaining functional groups into organic molecules are topics of continuous interest. Among different sulfur-containing compounds, vinyl sulfones often serve as the critical structural motifs in numerous pharmaceuticals and biologically active compounds. Given the great significance, considerable efforts have been exerted to develop efficient methods for the synthesis of these important frameworks. Except for the classic Knoevenagel condensation reaction, Horner-Wadsworth-Emmons olefination and vinyl sulfides oxidation reactions, atom transfer radical addition (ATRA) has emerged as a powerful strategy for the synthesis of vinylsulfone derivatives. A number of difunctionalization of alkynes, including halosulfonylation, 8 selenosulfonylation, 9 aminosulfonylation, 10 disulfonylation, thiocyanatosulfonylation, 12 carbosulfonylation 13 and carboxysulfonylation, have been developed through ATRA reactions. In sharp contrast, thiosulfonylation of alkynes has only rarely investigated, which allows concomitant formation of C-SO 2 and C-S bond in one step.