Isopropyl acetate and isopropyl alcohol were azeotropic mixtures with a minimum boiling point. To break the azeotrope of the above binary system and separate it, dibutyl ether and anisole were chosen as the extractive solvents in this corresponding extractive distillation process. Therefore, the vaporliquid equilibrium (VLE) measurements for (isopropyl alcohol + dibutyl ether), (isopropyl alcohol + anisole), (isopropyl acetate + dibutyl ether), and (isopropyl acetate + anisole) at 101.3 kPa were achieved by a modified Rose type recirculating still. The VLE data were checked by the van Ness test and pure component consistency test. The NRTL, UNIQUAC, and Wilson models were applied to correlate the determined VLE data. Furthermore, the suitability of entrainers was investigated by relative volatility and the effect of selected entrainers on the azeotrope. After that, the obtained binary interaction parameters can provide a basis for the simulation and optimization of the extractive distillation process.