The synthesis of methyl- and several aryl-thiovinyl arenesulphonates by addition of methane- and arene-sulphenyl arenesulphonates to diphenylacetylene, substituted diphenylacetylenes, and phenyl- and alkyl-acetylenes is reported. O-Sulphenyl arenesulphonates, like sulphenyl halides, give 1 : trans-adducts with acetylene derivatives. The structure of the adducts is discussed.