We report a cascade reaction of α-aryl vinyl and propargyl sulfonium salts with C-nucleophiles, resulting in the formation of functionalized benzyl and homoallyl thioethers, respectively, in good yields. In this novel reaction, a vinyl sulfonium derivative undergoes Michael addition with a C-nucleophile followed by [2,3]-sigmatropic rearrangement. This domino reaction is very general and takes place readily under mild conditions.