Continuous production of ethyl acetate involves various separation challenges due to multiple azeotropes. In this study, three-phase advanced distillation method is applied through diverse purification scenarios for ternary separation of ethyl acetate system (ethyl acetate/water/ethanol). This highly non-ideal mixture contains four azeotropes and three distillation regions. To select the best distillation region, the separation feasibility and conceptual design of ethyl acetate three-phase distillation unit are comprehensively investigated by the extended boundary value method for various feed locations and numerous product recoveries. It was found that the region in which ethanol is a stable component was the most suitable region for the distillation process. Further, the conceptual design of the three-phase column is optimized by variation of reflux ratio and operating pressure. Ultimately, based on the conceptual design results, rigorous simulation of the process is accomplished and ethanol is separated with 99.25 mol % purity.