AbstractA facile and efficient method to synthesize thioethers from sulfonyl chlorides and benzylic trimethylammonium salts is presented. This protocol provides a simple and direct approach to realize the reductive coupling reaction of readily available sulfonyl chlorides with benzyl ammonium salts in the presence of triphenylphosphine along with base via C−N cleavage of benzyl ammonium salts. This reaction features mild conditions and good substrate compatibility to afford thioethers in moderate to good yields.