A palladium-catalyzed coupling reaction of alkynylsulfones with alkenes has been described, which provides an efficient and practical entry to various functionalized dichlorinated vinyl sulfones. This method features excellent regio- and stereoselectivities, good functional group compatibility, as well as mild reaction conditions. Mechanistic studies suggest that the reaction goes through sequential syn-chloropalladation, alkene insertion, and C(sp3)-Cl bond formation processes, and the sulfonyl group is crucial to the stereoselectivity control of the reaction.