The separation of ternary mixtures that form multiple azeotropes is frequently encountered in industry. Benefiting from the pressure-sensitive nature of the azeotropic mixture, the pressure-swing distillation (PSD) is promising to realise the separation without introducing foreign solvents. However, the wide application of PSD seems challenging from an energetic point of view. This work has developed a sustainable PSD process with thermally and electrically coupled intensification to decrease energy consumption, taking the separation of homogeneous acetonitrile/ethanol/water mixture as a demonstrating example. Two conventional PSD processes with different product sequences are designed through the ternary phase diagram and further optimised using the NSGA-II, considering multiple objectives, including total capital cost, total operating cost, and CO2 emissions. The optimal solution is selected by the TOPSIS analysis for each sequence and is then intensified with thermal heat integration and electricity-driven heat pump techniques. The results show that, in comparison to the non-heat-integrated PSD process, the proposed intensified design can dramatically reduce the total annual cost by up to 48%, simultaneously decreasing CO2 emissions by up to 60% and boosting energy efficiency. The present study can be of reference for designing a sustainable PSD process in ternary azeotropic separation.