According to the characteristic of methyl acetate?methanol?water system in the presence of two kinds of azeotrope, three separation processes such as double solvent four column extractive distillation process, single solvent three column extractive distillation process and double solvent synergistic extractive distillation process were proposed on the basis of screening the extraction agent for the system. Energy consumption and total annual cost (TAC) as evaluation index, the simulations for the three separation processes were performed by Aspen Plus software which SR?Polar thermodynamic model was used to calculate phase equilibrium data and RadFrac model was used to simulate distillation column, and the optimal operating parameters and equipment parameters for the three separation processes were obtained. Simulation results showed that water and ethylene glycol were suitable extractant for the separation system, the single solvent three column extractive distillation process was better than the double solvent four column extractive distillation process and the energy consumption could be reduced by 37.9%, TAC decreased by 38.9%. Compared with the double solvent four column extractive distillation process and single solvent three column extractive distillation process, the double solvent synergistic extractive distillation process can save energy by 45.6% and 12.4%, reduce TAC by 43.5% and 11.6%, respectively.