The reaction of in situ generated arynes with aryl vinyl sulfoxides provides ortho-arylsulfinylaryl vinyl ethers via aryne σ-bond insertion into the S-O-bond and concomitant stereospecific S-O-vinyl migration. The cascade allows preparing di- or trisubstituted vinyl ethers with excellent stereospecificity. The reactions proceed under mild conditions, the substrate scope is broad, and the products obtained are valuable.