The exploitation of new materials for adsorptive separation of industrially important hydrocarbons is of great importance in both scientific research and petrochemical industry. Nonporous adaptive crystals (NACs) as a robust class of synthetic materials have drawn much attention during the past five years for their superior performance in adsorption and separation. Pillararenes are the main family of macrocyclic arenes used for NACs construction, where the structure–function relationship has been intensively studied. In the past two years, some emerging types of synthetic macrocyclic arenes have been successfully brought into this research field, showing the gradual enrichment and diversification of NACs materials. This Minireview summarizes the recent advances of synthetic macrocycle‐based NACs, which are categorized by various practical applications in molecular separation. Besides, NACs‐based vapochromic supramolecular systems are also discussed. Finally, future perspectives and challenges of NACs are given. We envisage that this Minireview will be a useful and timely reference for those who are interested in new molecular and supramolecular crystals for storage and separation applications. This Minireview describes the recent advances of synthetic macrocycle‐based nonporous adaptive crystals for molecular separation and vapochromic application.