The major intrinsic obstacle of extractive distillation (ED) is high energy consumption. Thus it is significant to reduce the energy consumption of ED processes as low as possible. In this work, using green solvent ILs which have high selectivity, process intensification and optimizing operation parameters are adopted in the ED of ethyl acetate-ethanol-water mixture. For high-selective entrainers, ionic liquid (IL) 1-butyl-3-methylimidazolium acetate ([bmim][OAc]) is used as the solvent for the ED process of ethyl acetate-ethanol-water, and the physical properties of [bmim][OAc] are accurately defined in Aspen Plus by correlating the experimental data. To optimize the distillation sequence for process intensification, thermally coupled ternary extractive distillation (TCTED) process is adopted for the separation of the ternary mixture. Moreover, multi-objective generic algorithm with total annual cost (TAC), CO2 emissions (E-CO2) and thermodynamic efficiency (eta) as objective functions is used to optimize the operation parameters in order to evaluate the economy, the energy efficiency and environmental impact of alternative ternary extractive distillation processes. The result shows that the TCTED process can result in the reduction of both TAC and E-CO2. So, this study can provide a reference for the separation of ethyl acetate-ethanol-water mixture in industry.