Multiple order self-diffractions by femtosecond laser-induced transient grating in CeO2 doped 75TeO2-20Nb2O5-5ZnO glass are investigated by pump-probe technique. The glass structure and component are investigated by Raman and visible-NIR absorption spectra. It is showed that there exists Ce3+ ion in tellurite glass, and the transient grating is created by the optical Kerr effects and improved by the excited particle grating from the resonant absorption of the 1S0 →1F3 electronic energy transition of Ce3+ ion, and the conversion efficiency of the first order diffraction signal reaches about 11%. The results indicate that CeO2 doped 75TeO2-20Nb2O5-5ZnO glass has potential applications in ultra-fast all-optical switching.