A synthetic strategy has been developed for the direct synthesis of ortho-methylthio allyl and vinyl ethers via three-component reaction of in situ generated aryne, activated alkene and DMSO. This reaction proceeds via several bond cleavage and bond formation processes in a single operation. Mechanistic studies reveal that DMSO served as both a methylthiolating agent and an oxygen source. This synthetic method provides a wide range of ortho-methylthio-substituted arenes in good yields.