Y3Al5O12(YAG):Ce3+ is the most widely applied phosphor in white LEDs (w-LEDs) because of strong blue absorption and efficient yellow luminescence combined with a high stability and thermal quenching temperature, required for the extreme operating conditions in high-power w-LEDs. The high luminescence quenching temperature (∼600 K) has been well established, but surprisingly, the mechanism for temperature quenching has not been elucidated yet. In this report we investigate the possibility of thermal ionization as a cause of this quenching process by measuring thermoluminescence (TL) excitation spectra at various temperatures. In the TL excitation (TLE) spectrum at room temperature there is no Ce3+:5d1 band (the lowest excited 5d level). However, in the TLE spectrum at 573 K, which corresponds to the onset temperature of luminescence quenching, a TLE band due to the Ce3+:5d1 excitation was observed at around 450 nm. On the basis of our observations we conclude that the luminescence quenching of YAG:Ce3+ at ...