An efficient, regioselective and steresoselecitive one-pot protocol for the synthesis of (Z)-S-2-alkoxycarbonyl-3-acylallyl ethanethioates and (E)-S-2-cyano-3-acylallyl ethanethioates from benzaldehydes and activated alkenes (methyl acrylate and acrylonitrile) was developed. Our method consisted of Morita–Baylis–Hillman reaction of benzaldehydes and activated alkenes using DABCO followed by acetylation using acetic anhydride and a catalytic amount of DMAP, and SN2′ reaction with potassium thioacetate in DMF. The first two reactions proceeded under solvent-free condition.