A copper-catalyzed vicinal chloro-thiolation of alkynes with inexpensive and diversified sulfonyl chlorides RSO 2 Cl (R = aryl, alkyl) has been developed. This practical and scalable reaction could be used for the construction of a number of unexplored bioactive chlorothiolated alkenes. Internal alkynes could also undergo the chloro-thiolation to provide tetrasubstituted alkynes. Preliminary mechanistic investigations revealed a plausible radical process involving a sulfur-centered radical intermediate via copper-mediated homolysis of the S−Cl bond.