Electron Donor–Acceptor Alignment in Matrix‐Engineered Carbon Dots for Minute‐Scale Persistent Luminescence

Carbon dots (CDs) have emerged as promising luminescent materials, yet their practical applications are hindered by short afterglow durations (typically seconds) and limited environmental stability. Here, we report a universal matrix‐engineering strategy that enables minute‐scale, multicolor afterglow in CDs by constructing an intramolecular charge‐transfer (ICT)‐driven electron donor–acceptor (D–A) system. Using tailored matrices of boric acid, silica, and cyanuric acid, we achieve robust host–guest interactions (e.g., hydrogen bonding, covalent linkage, and charge‐transfer states) that synergistically enhance confinement, stabilize triplet excitons, and promote long‐lived exciplex formation. The resulting composites exhibit ultralong afterglow with naked‐eye‐visible durations exceeding 240 s and a record lifetime of up to 300 s, alongside exceptional aqueous and thermal stability. Mechanistic studies reveal that pre‐existing ICT states in CDs facilitate electron‐cascade transfer, generating spatially separated charge‐separated states. Their delayed recombination bypasses spin‐forbidden decay pathways. We further demonstrate the versatility of these materials in dynamic information encryption, flexible films, and hydrogel‐based systems, highlighting their potential for advanced anti‐counterfeiting and smart displays. This work establishes a foundational framework for designing long‐persistent luminescent materials via molecular‐level D–A alignment, bridging the gap between organic and inorganic phosphors.