Using the electronic spectroscopy method, the laser-conoscopy method, and the Raman light-scattering method, we have studied the structural homogeneity of LiNbO3 crystals doped with 0.03–4.5 mol % of ZnO. We have found that, as the laser radiation power is increased to 90 mW, the conoscopic patterns of crystals show additional distortions, which are attributed to the manifestation of the photorefractive effect. For the LiNbO3 crystal doped with 4.5 mol % of ZnO, in which the photorefractive effect is low, we have revealed a considerable shift (compared to the remaining crystals) of the optical absorption edge toward the shortwavelength range, which indicates a high structural homogeneity of this crystal. We have shown that, in the LiNbO3 crystal doped by 0.05 mol % ZnO, due to the displacement of NbLi and Li□ structural defects by Zn2+ cations, the crystal structure is ordered and, simultaneously, the number of defects with localized electrons decreases.