In order to meet the high performance requirements of phosphors for high-power white light-emitting diode(LED), preparation and optical, electrical and thermal properties of CexGd∶YAG single crystals fluorescent materials for white LED were studied. The CexGd∶YAG (x=0.02, 0.04, 0.06, 0.08) single crystals were grown by the Czochralski method, and its luminescence properties were characterized via the XRD patterns, absorption and emission spectra. The temperature dependence of relative florescent light intensity and the performances of white LEDs fabricated by CexGd∶YAG single crystals with different Ce3+ concentration were also analyzed. The results indicate that when CexGd∶YAG crystal is excited by 450 nm blue light, a broad emission band of 500-650 nm range is produced, and the luminescence intensity is 10% higher than commercial phosphor at 100 ℃. When the Ce3+ concentration is 6%, the efficacy of white LED fabricated by CexGd∶YAG single crystals is up to 153 lm/W, more than twice the efficacy of white LED with Ce∶YAG-resin composite. CexGd∶YAG single crystals have higher and more stable florescent light intensity, and the efficacy of white LED has been greatly improved. CexGd∶YAG single crystals is expected to become a new type of commercial fluorescent material.