Mechanisms, Design Principles, and Emerging Strategies in Supramolecular Assembly‐Enabled Circularly Polarized Room‐Temperature Phosphorescence

ABSTRACT Circularly polarized luminescence (CPL) and room‐temperature phosphorescence (RTP) materials are crucial for advanced optoelectronic technologies, with applications in information encryption, 3D displays, and biomedical imaging. These materials integrate chiral optical activity with long‐lived emission, enabling multimodal optical functions. However, achieving both efficient CPL and RTP is challenging due to trade‐offs among emission efficiency, lifetime, and chiral intensity. Recent research shows that supramolecular self‐assembly provides diverse strategies to address these trade‐offs, allowing controlled chirality transfer, molecular packing, and emission regulation. This review highlights recent advances in CPP materials enabled by supramolecular self‐assembly strategies. By leveraging noncovalent interactions and supramolecular organization, these strategies modulate molecular conformation, rigidity, and intermolecular interactions to enhance CPL and RTP performance. Key approaches include chiral small‐molecule self‐assembly, host–guest inclusion, polymer–liquid crystal composites, coordination‐driven assembly, PSK‐based systems, and biomass‐derived assemblies. These methods provide pathways to achieve multicolor emission, tunable lifetimes, enhanced glum, and dynamic optical responses. Despite progress, challenges remain in structural complexity, processability, biocompatibility, and the lack of universal models to optimize g lum‐P and Φ P . Future work should focus on robust, scalable strategies for high‐performance, stable CPP materials, with a particular emphasis on supramolecular approaches for optoelectronics, security, and bioimaging.