The separation of ternary mixture of butanol, butyl acetate, and methyl isobutyl ketone(MIBK) was initially analyzed by the residual curve. In this process, MIBK was chosen as the azeotropic agent during the first step of separation. The optimum mass ratio of extra MIBK was 1.6 in the modified feed stream according to the residual curve. Thus on this condition the top product was butanol-MIBK azeotrope while the bottom product was butyl acetate in the preliminary separation of the mixture. Then the butanol and MIBK azeotrope was separated by the double effect pressureswing distillation with the low pressure column performing at 30 kPa and the atmospheric pressure column at 101 kPa. The optimal operating conditions were then obtained by using Aspen Plus to simulate and optimize the process. The results showed that the mass purities of butanol, butyl acetate, and MIBK were all more than 99% and reached the design requirements. Additionally, compared with the traditional distillation with outside heating, the double effect pressure swing distillation saved the reboiler duty by 48.6% and the condenser duty by 44.6%. The separation of ternary mixture of butanol, butyl acetate, and methyl isobutyl ketone (MIBK) was initially analyzed by the residual curve. In this process, MIBK was chosen as the azeotropic agent during the first step of separation. MIBK was 1.6 in the modified feed stream according to the residual curve. The top product was butanol-MIBK azeotrope while the bottom product was butyl acetate in the preliminary separation of the mixture. Then the butanol and MIBK azeotrope was separated by the double effect units with then low pressure column performing at 30 kPa and the atmospheric pressure column at 101 kPa. The optimal operating conditions were then obtained by using Aspen Plus to simulate and optimize the process. The results showed that the mass purities of butanol , butyl acetate, and MIBK were all more than 99% and reached the design requirements outside heating, the double effect pressure swing distillation saved the reboiler duty by 48.6% and the duty duty by 44.6%.