Multicomponent liquid mixtures, particularly azeotropes, are extensively utilized in the chemical, petroleum, pharmaceutical, and other processing industries. Energy-saving and efficient separation of azeotropes holds significant value for the design and development of sustainable industrial processes. Extractive distillation (ED) has consistently played a pivotal role in azeotrope separation. We offer a broad and comprehensive review that encompasses recent progress in multiple aspects of ED, including the screening of entrainers, process design, enhancement schemes, dynamic control strategies, and environmental assessment. Initially, we delved into the application of quantum chemistry calculations and molecular dynamics simulation for screening suitable entrainers. We then elucidate the design principles and forms of two distinct types of ED processes. Subsequently, we explore the intensification mechanisms of the ED process through coupling mechanisms, such as heat integration and the combination of ED with other distillation processes. We also summarize the recent improvements in dynamic control strategies for various ED processes. Lastly, we evaluate various aspects of ED from the perspectives of environmental impact, economic viability, and exergy analysis. This study investigates the challenges, prospects, and emerging trends of ED technology for the separation of multicomponent azeotropes.