The vapor-liquid equilibrium (VLE) and liquid-liquid equilibrium (LLE) of the ternary system of ethyl acetate + ethanol + 1-ethyl-3-methylimidazolium acetate ([EMIM][Ac]), together with the vapor-liquid-liquid equilibrium (VLLE) for the binary system of ethyl acetate + [EMIM][Ac], were measured. The experimental VLE, LLE, and VLLE data were correlated by the nonrandom two-liquid (NRTL) equation, and the calculated results agreed well with the experimental results. The VLE and VLLE results show that [EMIM] [Ac] can enhance the relative volatility of ethyl acetate to ethanol, and the azeotrope of ethyl acetate + ethanol can be eliminated. The LLE data indicate that [EMIM][Ac] is a potential solvent for the separation of ethyl acetate + ethanol via liquid-liquid extraction.