A Pd/norbornene/Cu cooperative catalysis for the efficient synthesis of 2-(arylthio)aryl ketones, from aryl halides and thioesters has been developed. The first example of cooperative catalysis by palladium, norbornene, and copper, wherein the C(O)-S bond of thioesters is cleaved by a Pd-II palladacycle with the assistance of CuI, has been observed.