In the face of the high energy consumption challenge in separating high-concentration organic waste liquid through extractive distillation (ED), the concept of preconcentration provides a new strategic direction. Therefore, it has become crucial to determine the suitability of the ED process with a preconcentration column for processing such complex mixture. Taking this into consideration, the study proposes an innovative quick-decision method that utilizes thermodynamic analysis of ternary phase diagram to determine the ratio of theoretical product flowrate at the bottom of the preconcentration column to the feed flowrate, which serves as the basis for deciding whether to choose the ED process with a preconcentration column for handling such separation tasks. Three azeotropic systems with different thermodynamic characteristics are chosen as case studies: cyclohexane/ethyl acetate/ethanol (Case 1), ethyl acetate/ethanol/water (Case 2), and n-hexane/ethyl acetate/acetonitrile (Case 3). The task of separating the above three systems is accomplished through the application of both three-column extractive distillation configuration (TCED), and four-column extractive distillation configuration (FCED). The objective functions for multi-objective optimization of all separation configurations include the minimum total annual cost (TAC), the minimum entropy generation and the minimum CO2 emissions. The research findings indicate that when the ratio of theoretical product flowrate at the bottom of the preconcentration column to the feed flowrate is not less than 0.56, or when there is a significant concentration difference among the components in the feed stream, the FCED configuration exhibits clear advantages over the TCED configuration in terms of economic, environmental, and thermodynamic aspects.