A direct and novel transformation of propargylic alcohols with sodium sulfinates for the regio- and stereoselective synthesis of (E)-1,3-disulfonylpropenes and (E)-1-sulfonylpropenols was successfully developed in the presence of TMSCl under mild conditions. The preliminary mechanistic experiments demonstrated that the reaction underwent an unprecedented dual nucleophilic substitution/radical addition process, in which sodium sulfinates were used not only as nucleophiles but also as a sulfonyl radical source.