The widespread use of lithium niobate (LN) in several technological applications, notably in optical and electrooptical systems, is a consequence of its remarkable piezoelectric, electrooptical, photoelastic, acousto-optic, and nonlinear optical coefficients. In this chapter, the structural and electrical characterization of LN nanosized particles synthesized by the Pechini route is discussed. Compared to solid-state reaction processes, wet chemistry processes can be advantageous alternatives for the synthesis of polycrystalline LN, because they require lower processing temperatures, and thus the loss of stoichiometry and formation of secondary phases can be minimized. The powders obtained by drying the gel (base powder) were heat-treated for 4 h at temperatures between 400 and 1000°C, according to the differential thermal analysis (DTA) results. It was found that the powders sintered at 450°C contain only the LN phase, while those heat-treated at 500°C already contain the secondary LiNb3O8 phase. The structural and electrical characterization of the samples sintered at 450°C, for different times, was performed using X-ray diffraction (XRD) in conjunction with Rietveld refinement, Raman spectroscopy, scanning electron microscopy (SEM), and impedance spectroscopy in the temperature range between 200 and 360 K and in the frequency range between 100 Hz and 1 MHz and by measuring the ac and dc conductivities.