Salt effect on vapor liquid equilibrium (VLE) for the toluene + methanol + N-butylpyridinium bromide system at 318.15 K and different salt concentrations (0.300, 0.700, 1.000, 1.200, and 1.500 mol.kg(-1)) has been determined by headspace gas chromatography. The azeotrope mixture of the toluene + methanol system can be broken by using N-butylpyridinium bromide. The experimental VLE data were correlated well with an electrolyte nonrandom two-liquid model.