The sustainability performance of extractive distillation (ED) that collectively considers energy efficiency, process safety, economic profitability, process control, and environmental emission has not been widely reported. Motivated by this lack of research, we analyzed and compared the sustainability performance of the intensified side-stream ED (SSED) with that of the conventional extractive distillation (CED) for the separation of binary azeotropic mixtures. Two different design approaches were analyzed; the first approach involves designing the intensified SSED by preserving the original CED column configuration, while the second approach involves optimizing the original column configuration to become a new intensified SSED configuration.