The hybrid distillation/crystallization process is successfully applied to separate azeotropes and closely boiling mixtures. This process can not only provide pure products, but also allow for significant energy savings. The research progress and industrial applications of hybrid distillation/crystallization are reviewed. Different sequences of hybrid distillation/crystallization process are presented based on the optimized design. The specific developments of each single unit, namely, distillation and crystallization, in the hybrid process are outlined. Applications of hybrid distillation/crystallization in practical cases are highlighted and analyzed. Finally, the key issues and perspectives for further research of this integrated process are illustrated.