Liquid-liquid equilibria for the ternary systems methyl acetate + methanol + octane and methyl acetate + methanol + nonane were studied at (278.15, 288.15, and 298.15) K and at atmospheric pressure. Composition analysis of each phase was carried out by gas chromatography. The nonrandom two-liquid and universal quasichemical models were used to correlate the experimental results. A good fit has been obtained as a function of temperature for all cases studied. The UNIFAC group contribution method and its modifications have been applied to test their prediction capability. A poor prediction was observed from the contribution methods.