Abstract Copper(I) trifluoromethylthiolate complex (PPh3)2Cu(SCF3) (1) has been synthesized from a convenient reaction of CuF2 with CF3SiMe3 and S8 in the presence of triphenylphosphine. The crystal structure of complex 1 has been determined by X-ray crystallography. In the solid state, complex 1 exists as a monomeric copper(I) species with a three-coordinated trigonal planar geometry. Complex 1 reacted with a wide range of allylic bromides to afford corresponding allylic trifluoromethyl thioethers in moderate to good yields. Several functional groups, including alkyl, alkoxy, nitro, halides and geranyl groups, are tolerated.