A mixture of organic solvent and ionic liquid (IL) was proposed as entrainer for the ethanol/water separation by extractive distillation. The vaporliquid equilibrium (VLE) experimental results showed that the relative volatility of ethanol to water is significantly enhanced using the ethylene glycol (EG) and [EMIM](+)[Ac]- mixed entrainers when compared to that of the benchmark solvent EG. The nonrandom-two-liquid model parameters were correlated using the measured ternary and quaternary experimental VLE data. On this basis, process simulation was carried out to evaluate the improvement of the proposed mixed entrainers. It was found that for the ethanol/water separation using the mixed entrainers, the overall heat duties on reboilers in the processes without and with heat integration (HI) decrease 11.53% and 10.34%, respectively, when compared to the conventional benchmark solvent EG. Moreover, the presented process intensification method is easily achieved in practice by substituting the proposed mixed entrainers for the conventional solvent without changing the whole flowsheet.