Single crystals of lithium niobate (LiNbO3), possessing high birefringence and anisotropic properties have been explored, for a long time, to harness their excellent electro-optic properties. However, their nanoforms are comparatively less explored. In this context, dielectric constant and polarization (P) versus electric-field (E) characteristics of LiNbO3 nanomaterials have been studied. A nonideal P-E loop and a dielectric constant of 20 at the onset of 1 kHz were seen. The electro-optic sensitivity was found to be 4 times as compared to the bulk LiNbO3 crystals. The results are attributed to oxygen vacancies, antisite defects, and grain boundary effects in an already congruent structural matrix of LiNbO3.