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Materials with ultralong phosphorescence have wide-ranging application prospects in biological imaging, light-emitting devices, and anti-counterfeiting. Usually, molecular phosphorescence is significantly quenched with increasing temperature, rendering it difficult to achieve high-efficiency and ultralong room temperature phosphorescence. Herein, we spearhead this challenging effort to design thermal-quenching resistant phosphorescent materials based on an effective intermediate energy buffer and energy transfer route. Co-crystallized as