A systematic design and optimization method for vinyl acetate/acetic acid/acetic anhydride ternary system separation processes is proposed. Herein, four separation schemes including the conventional distillation, the inter‐column mechanical vapor recompression heat pump distillation (IMVRHP), the double mechanical vapor recompression heat pumps distillation (DMVRHPs), and DMVRHPs with heat exchange network (DMVRHPs‐HEN) are conducted. The optimal separation process is determined by minimizing the total annual cost (TAC) and CO2 emission. As a result, the three designed mechanical vapor recompression heat pump distillation (MVRHP) processes show better performance in all aspects than conventional distillation process. Specifically, the DMVRHPs‐HEN scheme saves 89.75% of the CO2 emission and 0.09% of the TAC compared with conventional distillation process. More important, the TACs of DMVRHPs‐HEN are decreased by 22.21% and 57.69% compared with those of conventional distillation process when the payback period is 5 and 8 years, respectively. This research is expected to provide theoretical guidance for the energy saving scheme of vinyl acetate/acetic acid/acetic anhydride ternary system.