This paper reports the results of a new experimental study of liquid-liquid equilibria for the mixtures methyl acetate + methanol + hexane or heptane at atmospheric pressure and at (268.15, 278.15, 288.15, and 298.15) K. The equilibrium compositions were measured by gas chromatography from samples split isothermally into a glass-stirred device, and phase diagrams are reported at each temperature. The experimentally determined liquid-liquid equilibria were satisfactorily correlated by the NRTL and UNIQUAC equations. A comparative analysis was performed by application of UNIFAC group contribution method and its modifications to predict experimental liquid-liquid equilibria (LLE) behavior of these ternary mixtures. A poor prediction was observed from these contribution methods.