We developed the regioselective anti-carbometalation of alkynyl sulfides via the use of InBr3 and organosilicon nucleophiles to give beta-mercaptoalkenylindium compounds. The structure of beta-mercaptoalkenylindium was characterized by X-ray crystallographic analysis. A variety of disubstituted alkenyl sulfides were regio- and stereoselectively obtained by either halogenation or Pd-catalyzed cross-coupling with aryl halides using the mercaptoalkenylindiums.