Vapor-liquid equilibrium (VLE) and liquid-liquid equilibrium (LLE) were measured for the ternary system of methyl acetate + methanol + 1-ethyl-3-methylimidazolium acetate ([EMIM][Ac]). The experimental LLE data were correlated by the NRTL model and the binary interaction parameters obtained from LLE were used to predict the ternary V:LE, and the results agreed well with the experimental data. The results showed that the ionic liquid ([EMIM][Ac]) produced a notable salting-out effect, which enhanced the relative volatility of methyl acetate and methanol.