A novel method for the Cu(OAc)2 catalyzed synthesis of unsymmetrical sulfides from triphenyltin chloride and aryl halides using S8 as the sulfur source in PEG200 at 60–80 °C is reported. Triphenyltin chloride is capable of delivering all of its phenyl groups to the product. Also, the copper catalyzed synthesis of symmetrical diaryl sulfides from aryl halides using S8 is described.