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A straightforward and efficient synthesis of a,ß-unsaturated thioesters has been developed via a nickel-catalyzed thiocarbonylation reaction of vinyl triflates with arylsulfonyl chlorides. With Mo(CO)6as both CO source and reductant, a variety of a,ß-unsaturated thioesters were obtained in moderate to good yields with very good functional group compatibility. It is noteworthy that the present method is the first example on nickel-catalyzed carbonylative synthesis of a,ß-unsaturated thioesters by using arylsulfonyl chlorides as the coupling partner.