RhH(PPh3)4 and 1,2-bis(diphenylphosphino)benzene (dppBz) catalyze the aryl exchange reaction of polyfluorinated diaryl sulfides. By employing these catalysts, unsymmetrical polyfluorinated diaryl sulfides are synthesized by the reaction of symmetrical polyfluorinated diaryl sulfides and substitutedpentafluorobenzenes in the presence of triisopropylsilane.