Abstract In recent years, chiral discrete supramolecular coordination complexes have attracted increasing interest as simple enzyme mimetics owing to their aesthetic architectures and potential applications in chiral science. This review summarizes the recent advances on chiral coordination metallacycles/metallacages with inherent cavities for enantionselective recognition and separation, including their design principles and synthesis, the introduction of chirality and functionality, structural adaptability, and host‐guest bonding in enantioselective process. Finally, the perspectives on the remaining challenges and future opportunities are presented.