Precise　control　over　the　release　of　light　energy,　distinct　from　conventional　thermal　energy　management,　poses　significant　challenges　in　luminescent　technologies.　This　study　pioneers　organic　above-room-temperature　thermoluminescent　materials　using　radical　pairs　as　energy　storage　centers　(ESCs),　enabling　controlled　light　energy　release　from　multi-hour　afterglows　to　microsecond-scale　explosive　bursts,　accelerating　the　energy　release　rate　by　up　to　1.8　x　108　times.　Notably,　the　unique　transannular　interactions　between　sulfur　and　oxygen　in　thianthrene　oxides　facilitate　a　thermally　driven　back　electron　transfer　(BET)　process　based　on　radical　pairs,　central　to　the　energy　storage　and　release　mechanism.　Due　to　this　BET　process,　these　materials　precisely　modulate　luminescence　and　exhibit　robust　stability,　maintaining　luminescence　for　4　h　in　boiling　water　and　storing　energy　in　air　for　over　six　months.　These　findings　advance　organic　thermoluminescence,　highlight　the　significance　of　BET　processes　in　various　domains,　and　set　new　performance　benchmarks　for　luminescent　materials　under　extreme　conditions.