Herein, a one-step chlorosulfonylation of alkynes via a photocatalytic redox process is described. A variety of commercially available sulfonyl chlorides can be applied for the generation of sulfonyl radical species under visible-light irradiation. Regio- and stereoselective addition of the sulfonyl radical and chloride leads to the efficient formation of ( E)-selective β-chlorovinyl sulfones from a broad range of terminal and internal alkynes. The reported method represents an operationally simple and mild way to furnish vinyl sulfones.