A series of aAl5O12:Ce (YAG:Ce) phosphors doped with different Si4+ concentrations is prepared by solid-state reaction. The temperature dependent characteristics of luminescent spectrum and decay time of Ce3+ are investigated. With Si4+ doped, the emission spectrum shows a blue shift clue to a decrease of the splitting of 5d levels of Ce3+ ion. The thermal stability is greatly improved by adding Si4+ because the activation energy AE increases from 0.1836 eV to 0.2401 eV. The study of the decay times against temperature for various doping concentrations of Si4+ shows that the calculated nonradiative decay rate is affected by Si4+ substitution. The results are explained by the configurational coordinate diagram.