N-amyl alcohol, n-amyl formate, n-propanol and n-propyl formate are all organic solvents with important industrial application value. In industrial production, related alcohol ester azeotropic systems are often generated. Therefore, it is necessary to study the refining process of these substances. The work designed purification processes for two different azeotropic systems of alcohol esters via extractive distillation and pressure swing distillation methods. The required binary interaction parameters were obtained through vapor–liquid equilibrium experiments. Based on experimental data, a suitable entrainer was determined through different methods of analysis. The processes were optimized with the economic cost as the objective. In addition, it evaluated and analyzed different processes from multiple perspectives. This work explores the purification process of alcohol ester systems, providing theoretical guidance for achieving efficient separation of alcohol ester systems.