For separation of the azeotrope of allyl alcohol and water, three extractive agents-isobutyl acetate, butyl acetate, and butyl propionate were selected to extract allyl alcohol from the azeotrope. To recover the extractive agents by distillation, the isobaric vapor-liquid phase equilibrium (VLE) data for allyl alcohol + isobutyl acetate, allyl alcohol + butyl acetate, and ally' alcohol + butyl propionate were measured at 101.3 kPa. With the VLE data, there is no azeotrope formed in three systems. The consistency of the measured VLE data was validated by the Herington, infinite dilution, pure component consistency, and van Ness tests. Moreover, the Wilson, UNIQUAC, and NRTL models were used to fit the measured VLE data. All of the calculated results agreed with the VLE experimental data. Meanwhile, the parameters of the Wilson, UNIQUAC, and NRTL were regressed, which can be employed for the development and optimization of the separation process. Furthermore, the VLE data were predicted by the UNIFAC model for the three binary mixtures, and better prediction values were presented.