Three ionic liquids (ILs) (1-ethyl-3-methylimidazolium bromide, [EMIM]Br; 1-ethyl-3-methylimidazolium chloride, [EMIM]Cl; and 1-ethyl-3-methylimidazolium acetate, [EMIM][Ac]) were used for the separation of the ethyl acetate + methanol azeotropic mixture. The vapor-liquid equilibrium (VLE) data of ethyl acetate + methanol azeotropic mixtures containing ILs were measured at 101.3 kPa. The three ILs show significant salting-out effects on ethyl acetate. The azeotropic point of the ethyl acetate + methanol azeotropic system is eliminated when the mole content of IL reaches a special value. The separation abilities of the three ILs follow the order [EMIM][Ac] > [EMIM]Cl > [EMIM]Br. The experimental data are correlated well by the nonrandom two-liquid model.