Zn∶Mn∶Fe∶LiNbO3 crystals with 1%, 3%, 5%, 7% and 9%, ZnO(in mole) and MnCO3 and Fe2O3, added at concentration of 0.03%and 0.08(in mass)respectively, were grown by Czochralski method from congruent LiNbO3 melting. The OH- infrared absorption spectra, the optical damage resistance and phase conjugate properties of Zn∶Mn∶Fe∶LiNbO3 crystals were tested. When Zn2+ concentration reaches 7% and 9%, OH- absorption peaks shift to 3 528 cm-1. The mechanism of OH-1 absorption peaks shift were discussed. The optical damage resistance ability of Zn∶Mn∶Fe∶LiNbO3 crystals increase, with the increase of Zn2+ concentration. When Zn2+ concentration reaches to 7% (reaches threshold value), the optical damage resistance ability are two orders of magnitude higher than that of LiNbO3 crystals. The enhancement mechanism of optical damage resistance of highly doping zinc Mn:Fe: LiNbO3 crystals was researched. The bhase conjugate reflectivity decreases and phase conjugate response speed increases, with the increase of Zn2+ concentration. The phase conjugate mirror has eliminate optical wave phase distortion. The holographic associative storage experiment was carried out using Zn∶Mn∶Fe∶LiNbO3 crystals as storage medium. The working principle of holographic associative storage was discussed. Using 25% and 50% addressing, the intact storage image was received in output plane.