Organic molecules and polymers have recently been intensively explored for afterglow materials owing to their low cost and flexible design. However, they normally fail to generate long-persistent luminescence at elevated temperatures, mostly due to the fast deactivation of triplet excited states. Here, we report that polycyclic aromatic compounds (PACs) individually confined in a B2O3 crystalloid emit long-persistent luminescence at high temperatures up to 400 °C. This is facilely accomplished by dispersing a series of aromatic derivatives in an aqueous solution of boric acid, followed by drying, melting, and dehydrating. The resulting highly rigid and thermostable B2O3 crystalloid network provides a matched ultrastrong confinement effect and completely restricts the vibration and rotation of the molecularly distributed PACs even at ultrahigh temperatures and thereby prevents the nonradiative dissipation of triplet excitons and promotes the generation of ultrahigh-temperature long-persistent luminescence. The afterglow colors are responsive to both temperature and time, spanning from ultraviolet to near-infrared regions over a wide temperature range, which is substantially modulated by the subtle balance of phosphorescence and thermally activated delayed fluorescence. These features favor the creation of advanced afterglow materials for visual 3D temperature probing, anticounterfeiting, and data encryption in extreme environments.