Near-stoichiometric LiNbO3 single crystals codoped with Zn and Fe (Zn:Fe:NSLN) were grown by Czochralski (CZ) method using Li-rich melts. Structure analysis was performed by the X-ray powder diffraction and ultraviolet–visible (UV) absorption spectra in these samples. Experimental results showed that the lattice constant values increased with the increasing ZnO content in melt and ultraviolet absorption edge shifts to the shorter wavelength when compared with pure near-stoichiometric sample in Zn:Fe:NSLN. In addition, the optical damage resistance was also measured, which was several order of magnitude increased when compared with near-stoichiometric LiNbO3:Fe (Fe:NSLN) crystal. Holographic experiments were performed to analyze quantitatively the enhancement of the optical damage resistance.