The article reports a molecular design strategy using a hybrid perovskite (TpyBiCl₃) to overcome thermal quenching in X-ray scintillators. The structure of the perovskite provides a platform to modulate luminescence centers, with the rigid framework stabilizing triplet states, leading to a 45% increase in room-temperature phosphorescence quantum yield compared to its organic ligand (Tpy). The interactions between the organic and inorganic components enable the mixing of different excited states, resulting in temperature-responsive multi-emissions. The TpyBiCl₃ scintillator exhibits a detection limit of 38.92 nGy s⁻¹ at 213 K and 196.31 nGy s⁻¹ at 353 K, demonstrating the potential to mitigate thermal quenching in X-ray scintillators by tuning different excited states. The study advances the development of efficient scintillators for use in abnormal environments.The article reports a molecular design strategy using a hybrid perovskite (TpyBiCl₃) to overcome thermal quenching in X-ray scintillators. The structure of the perovskite provides a platform to modulate luminescence centers, with the rigid framework stabilizing triplet states, leading to a 45% increase in room-temperature phosphorescence quantum yield compared to its organic ligand (Tpy). The interactions between the organic and inorganic components enable the mixing of different excited states, resulting in temperature-responsive multi-emissions. The TpyBiCl₃ scintillator exhibits a detection limit of 38.92 nGy s⁻¹ at 213 K and 196.31 nGy s⁻¹ at 353 K, demonstrating the potential to mitigate thermal quenching in X-ray scintillators by tuning different excited states. The study advances the development of efficient scintillators for use in abnormal environments.