The well crystalline YAG:Ce3+ phosphor was synthesized by solid-state method, and the temperature dependence of excitation and emission spectra of YAG:Ce3+ phosphor were investigated in the temperature range from room temperature to 573 K. With temperature increasing, it was noted that the emission intensity of as-prepared phosphors decreased considerably more rapidly when pumped by 460 nm than by 340 nm. The temperature-intensity curves under different excitation wavelengths were obtained using an Arrhenius function, and the corresponding activation energies were also obtained respectively. Thus, the experimental phenomenon was discussed in terms of nonradiative decay rate. The effects of as-prepared phosphors on the performance of the white LED with changing temperature were also studied.