Potassium permanganate (KMnO 4) oxidizes quaternary ammonium bromides to the corresponding tribromides conveniently and effectively. The procedure adopted is environmentally friendly as it is solvent-free. High purity, excellent yield, shorter reaction time and mild reaction conditions are some of the advantages of this synthetic protocol. The efficacy of quaternary ammonium tribromides, especially benzyltrimethylammonium tribromide, is also studied for bromination of some organic substrates.