Ce:Fe:LiNbO₃ crystals were processed with oxidized and reduced method. The crystal composition and defect structure were analyzed by the Ultraviolet(UV)-Visible(Vis) absorption and Infrared(IR) transmission spectroscopy. The photo-damage resistance ability of the samples was observed by straightly observing the transmission facula distortion method. The results show that the photo-damage resistance ability of sample with growth state is essentially one magnitude higher than one with reduced state，and photo-damage resistance ability of sample with oxidation state is two magnitudes higher than one with reduced state. The photorefractive properties of the samples are experimentally studied by using the two-wave coupling method. The results of the two-wave coupling experiments show that from oxidation state to growth state to reduction state of the samples，the diffraction efficiency decrease but the response time is shorten and the photorefractive sensitivity increase while the dynamic range decrease slowly.