For separation of the azeotrope (methanol + methyl acetate), extractive distillation is applied and isobutyl acetate, isopentyl acetate, and p-xylene are chosen as the entrainers. To obtain the binary interaction parameters of thermodynamic models for design of the extractive distillation process, the isobaric vapor-liquid equilibrium (VLE) data for the three binary systems of (methyl acetate + isobutyl acetate), (methyl acetate + isopentyl acetate), and (methyl acetate + p-xylene) were determined at the pressure of 101.3 kPa. The thermodynamic consistency for the VLE experimental data of the three mixtures were tested by the Herington and van Ness methods. The NRTL, UNIQUAC, and Wilson thermodynamic models were adopted to correlate the VLE experimental data, and the binary interaction parameters of the three models were regressed.