Researchers have developed stable and ultralong room-temperature phosphorescent (RTP) copolymers with excellent adhesion, resistance, and toughness. These materials are based on polyvinyl butyral resin (PVB) with a balance of mutually exclusive features, including a rigidly hydrophilic hydrogen bond network and elastically hydrophobic constituent. By doping rigid triphenylene derivatives (TpB and TpBe) into the PVB matrix, they achieved ultralong RTP emission with lifetimes up to 5.82 seconds and a blue afterglow lasting over 30 seconds. These materials exhibit reversible photoactivated RTP, maintaining bright afterglow under various conditions, including exposure to water and mechanical stress. They also demonstrate strong adhesive properties and excellent water resistance, making them suitable for applications such as in situ modulated anticounterfeit labels and as adhesives for explosion-proof glass. The materials' enhanced mechanical properties, including high tensile strength and toughness, further enhance their practical utility. The study provides insights into developing stable, ultralong RTP materials with desirable performance.Researchers have developed stable and ultralong room-temperature phosphorescent (RTP) copolymers with excellent adhesion, resistance, and toughness. These materials are based on polyvinyl butyral resin (PVB) with a balance of mutually exclusive features, including a rigidly hydrophilic hydrogen bond network and elastically hydrophobic constituent. By doping rigid triphenylene derivatives (TpB and TpBe) into the PVB matrix, they achieved ultralong RTP emission with lifetimes up to 5.82 seconds and a blue afterglow lasting over 30 seconds. These materials exhibit reversible photoactivated RTP, maintaining bright afterglow under various conditions, including exposure to water and mechanical stress. They also demonstrate strong adhesive properties and excellent water resistance, making them suitable for applications such as in situ modulated anticounterfeit labels and as adhesives for explosion-proof glass. The materials' enhanced mechanical properties, including high tensile strength and toughness, further enhance their practical utility. The study provides insights into developing stable, ultralong RTP materials with desirable performance.