Extractive distillation is commonly used for the separation of azeotropic or close-boiling mixtures in the chemical industry. During the past decade, the use of ionic liquids (ILs) as entrainers has received considerable attention due to their unique advantages when applied in extractive distillation. This work is devoted to providing an easy-to-read and comprehensive review on the recent progress made by chemical engineers, focusing on the issues of predictive thermodynamic models, structure-property relations, separation mechanisms, and process simulation and optimization. This review spans from the molecular level to the industrial scale, to provide a theoretical insight into the molecular interactions between ILs and the components to be separated. Moreover, a comprehensive database on the vapor-liquid equilibria (VLE) and activity coefficients at infinite dilution concerning ILs is provided as Supporting Information. Concluding remarks are made on the unsolved scientific issues with respect to this promising special distillation technology.