Natural polymers are attractive matrices for sustainable phosphorescent materials, yet their hydrated and dynamically disordered networks poorly stabilize triplet excitons, particularly at elevated temperatures. Here we report a bioinspired protein-ordering confinement (POC) strategy by embedding 9H-dibenzo[a,c]carbazole (CZ) in silk fibroin (POC-SF), inspired by the disorder-to-order transition of tardigrade protective proteins. Ethanol-induced high β-sheet content (ϕ_β) creates a dehydrated, densely hydrogen-bonded network that suppresses molecular motion and non-radiative decay. The resulting POC-SF exhibits an ultralong room-temperature phosphorescence (RTP) lifetime of ~4.4 s and a visible afterglow of ~30 s at room temperature, while retaining high-temperature phosphorescence (HTP) lifetimes above 150 ms at 433 K. Variable-temperature infrared spectroscopy, transient-absorption measurements and molecular dynamics simulations link this thermal persistence to restricted protein-chain dynamics and more frequent short-range SF-CZ contacts. Together, these changes are consistent with fewer configurational pathways for non-radiative decay. Furthermore, multicolor RTP and HTP are achieved by incorporating commercial fluorescent dyes. A deep-learning model inversely designs temperature-time conditions for target phosphorescent outputs, which are experimentally validated to establish a closed loop. This work establishes POC as a tunable confinement mechanism for sustainable, thermally robust afterglow materials with applications in encryption, anti-counterfeiting, thermal-history recording and high-temperature information storage.
 

RTP,HTP,bioinspired materials