Herein, a metal-free main-group catalysis system for thiosulfonylation of terminal alkynes with thiosulfonates has been established by using commercially available B(C6F5)3 as a catalyst. The protocol provides a highly regio- and stereoselective route for the synthesis of diverse (E)-(β)-arylthiolvinyl sulfones under mild conditions with 100% atom-economy and exceptional functional group compatibility.