A B S T R A C TIsobaric vapor-liquid equilibrium (VLE) data for ternary systems of methyl acetate + methanol containing three ionic liquids (ILs) were measured at 101.3 kPa. The investigated ILs were 1-hexyl-3-methylimidazolium chloride ([HMIM][Cl]), 1-benzyl-3-methylimidazolium chloride ([BzMIM][Cl]), and 1-hexyl-3-methylimidazolium bromide ([HMIM][Br]). The results indicate that the addition of ILs can give rise to the increase of the relative volatility of methyl acetate to methanol. Besides, the more ILs, the larger the relative volatility. All the three investigated ILs can eliminate the azeotropic point of methyl acetate and methanol, and the separation effect follows the order: [HMIM][Cl] > [BzMIM][Cl] > [HMIM] [Br]. Additionally, the measured VLE data are well correlated with NRTL model.