A new energy-saving process is proposed here for the co-production of ethyl acetate (EtAC) and amyl acetate (AmAC) by reactive distillation(RD). The thermodynamic feasibility of the ethyl acetate/amyl acetate system was determined based on its physical properties. As amyl acetate has a higher water-carrying capacity than ethyl acetate, water can be removed from the reaction system in the form of azeotrope to improve the conversion rate, and amyl acetate can be easily separated from the water. The reactive distillation process of ethyl acetate-amal acetate co-production with different alcohol feed ratios was studied in this paper. When the amyl alcohol to ethanol feed mole ratio was set at 2, the process performed better in terms of economy and energy consumption; it also had a less environmental impact at the same time. The reactive distillation process with intermediate condenser and intermediate reboiler (RD-IC-IR) process and the reactive dividing-wall column (RDWC) process are established based on process optimization. Compared with the RD process, the TAC and CO2 emissions for the RD-IC-IR process reduced by 21.92 % and 28.27 %, respectively, and the thermodynamic efficiency improved 38.86 %; the TAC and CO2 emissions for the RDWC process reduced by 36.11 % and 42.49 %, respectively, and the thermodynamic efficiency improved 74.45 %.