ABSTRACT Organic room‐temperature phosphorescent (RTP) materials, characterized by their prolonged emission durations, cost‐effectiveness and environmental sustainability, present substantial potential for utilization in optoelectronic devices and information encryption, thereby garnering considerable research attention. Nevertheless, the intrinsically weak spin–orbit coupling (SOC) in organic molecules hampers efficient intersystem crossing (ISC) between singlet and triplet states, thereby shortening the lifetime (τ) of RTP. Achieving room‐temperature phosphorescence in organic molecules hinges on overcoming two fundamental challenges: promoting efficient ISC between singlet and triplet states and suppressing non‐radiative decay through rigid microenvironmental confinement. This review summarizes recent advances in pure organic RTP from the perspective of multicomponent systems, highlighting emerging strategies for modulating exciton dynamics and rigidifying the local environment of emissive molecules. Approaches such as supramolecular self‐assembly, guest–host doping, eutectic formation and exciplex engineering are discussed as effective means to suppress non‐radiative deactivation and realize ultralong RTP (emission lifetime of over 100 ms). The underlying design principles and representative applications of these systems are delineated, and future directions for constructing high‐performance pure organic RTP materials are outlined. Our goal is to foster interdisciplinary collaboration and innovation to fully exploit the potential of RTP materials in organic optoelectronics and biomedicine. This review aims to delineate a coherent research trajectory and offer forward‐looking insights into emerging opportunities in this rapidly evolving field. By promoting cross‐disciplinary dialogue to catalyze new ideas and applications that harness the unique photophysical characteristics of RTP materials for transformative technological advancements.
Zhou et al. (2026) studied this question.