© 2015 American Chemical Society. 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 high temperatures is caused by the thermal ionization and not by the thermally activated cross over to the 4f ground state. The conclusion is confirmed by analysis of the positions of the 5d states of Ce3+ relative to the conduction band in the energy band diagram of YAG:Ce3+.