The paper reports the development of stable and ultralong room-temperature phosphorescent (RTP) copolymers with excellent adhesion, resistance, and toughness. The researchers used polyvinyl butyral resin (PVB), a random copolymer derived from polyvinyl alcohol (PVA), as the matrix, which contains a balance of mutually exclusive features, including a rigidly hydrophilic hydrogen bond network and an elastically hydrophobic constituent. By doping rigid triphenylene derivatives (TpB and TpBe) into the PVB matrix, they achieved RTP films with superior adhesive ability on various surfaces and reversible photoactivated RTP with lifetimes up to 5.82 seconds. These films can maintain a bright afterglow for over 25 seconds under practical conditions, such as storage in refrigerators, soaking in natural water for a month, or even being subjected to strong collisions and impacts. The findings provide insights into developing stable and robust RTP materials with desirable comprehensive performance, making them suitable for applications in information encryption, anticounterfeiting technology, and other areas.The paper reports the development of stable and ultralong room-temperature phosphorescent (RTP) copolymers with excellent adhesion, resistance, and toughness. The researchers used polyvinyl butyral resin (PVB), a random copolymer derived from polyvinyl alcohol (PVA), as the matrix, which contains a balance of mutually exclusive features, including a rigidly hydrophilic hydrogen bond network and an elastically hydrophobic constituent. By doping rigid triphenylene derivatives (TpB and TpBe) into the PVB matrix, they achieved RTP films with superior adhesive ability on various surfaces and reversible photoactivated RTP with lifetimes up to 5.82 seconds. These films can maintain a bright afterglow for over 25 seconds under practical conditions, such as storage in refrigerators, soaking in natural water for a month, or even being subjected to strong collisions and impacts. The findings provide insights into developing stable and robust RTP materials with desirable comprehensive performance, making them suitable for applications in information encryption, anticounterfeiting technology, and other areas.