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In the era of intelligence, the output colors of foundational phosphors are expected to be controlled by programs, while current activators‐determined afterglow candidates with fixed spectral channel have limitations in creating customized colors. Here, a long‐lived warm‐white emission is successfully demonstrated originating from self‐trapped excitons (STEs) in non‐toxic Cs2NaInCl6:Ag,Bi, ranging from 400 to 850 nm, of which the afterglow color can be easily customized using filters. This investigation indicates that 3% of Ag alloying breaks the dark STEs and introduces traps for efficient afterglow, while 3% Bi doping further improves the quantum yield to ≈100% and greatly enhances afterglow by ≈100‐fold compared with the initial intensity, allowing for an impressive afterglow persistence of over 20,000 s. Intriguingly, the self‐trapped defect bands from Jahn‐Teller distortions are prolonged from hundreds of femtoseconds to several hours, and they are first detected in the steady‐state absorption spectra after the cessation of excitation sources, contributing to the concluded dynamic afterglow model for STEs. And its intelligent application is corroborated by designed multi‐channel information system. These findings offer a novel scheme for understanding dynamic luminescence of STEs and supply an exemplification of designing white afterglow phosphors. [ABSTRACT FROM AUTHOR]

The "hot exciton" mechanism based on high-lying reverse intersystem crossing process has great advantages in achieving high-performance deep-blue organic light-emitting diodes (OLEDs). Nevertheless, how to solve the loss of high-lying excitons to improve device performance further is a pressing and challenging issue. To break through this shackle, a novel deep-blue emitter based on "exciton recovery" strategy is successfully design, namely CAT. By combining the transient absorption spectrum, theoretical calculation, magneto-electroluminescence, and transient-electroluminescence measurements, the multi-channeled pathways of excitons utilization via hot exciton and triplet-triplet annihilation processes is comprehensively demonstrated, and the proportion of singlet excitons by each channel. Finally, a high exciton utilization efficiency is successfully achieved, and the non-doped OLED based on CAT exhibit an excellent external quantum efficiency of 10.39% with the CIE coordinates of (0.15, 0.087). Furthermore, the sensitized blue fluorescent OLED by CAT as host also achieves excellent performance. More importantly, the operational lifetime of the "multi-channel" sensitized device is evaluated for the first time, performing the remarkable LT50 (lifetime to 50% of the initial luminance) of 320 h at 540 cd m-2. These results fully reveal the significance of the "exciton recovery" strategy and give new inspiration for exploring highperformance blue OLEDs. [ABSTRACT FROM AUTHOR]