A convenient synthesis of $\alpha$ -alkyl (or aryl) thio substituted vinyl phosphonates has been studied. $\alpha$-chloro- $\alpha$ -sulfenyl phosphonates were prepared by direct chlorination of $\alpha$ -sulfenyl phosphonates with N-chlorosuccinimide (NCS). Treatment of $\alpha$ -chloro- $\alpha$ - sulfenyl phosphonates with Lewis acids affords the corresponding vinyl phosphonates in good yields under mild conditions.