Novel wet-chemical methods of synthesis have been adopted to synthesize nano-crystalline CeO2 and Gd-substituted compositions aiming to explore an efficient oxide ion conducting solid electrolyte for intermediate temperature solid oxide fuel cell (IT-SOFC) applications. Nano-crystalline CeO2 powders were synthesized by combustion method using redox mixture of cerric ammonium nitrate or cerium nitrate and maleic acid or 1,3-dimethylurea and compared with high surface area CeO2 powders prepared by hydrothermal technique with microwave precipitated precursor from aqueous solutions of (NH4)(2)Ce(NO3)(6) and urea. The grain size achieved by the hydrothermal technique is similar to 7 nm which is smaller than that of commercial nano CeO2 powders. Conventional or microwave sintering was used to prepare dense Ce0.8Gd0.2O1.9 pellets from the ceria powders made of redox mixture of cerium nitrate, 1,3-dimethylurea (DMU) and Gd2O3 as the starting ingredients. The samples were characterized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and ac impedance spectroscopy. The ionic conductivity measured for the pellet sintered at 1400 degrees C is 1 x 10(-2) and 2.4 x 10(-2) S/cm at 700 degrees C and 800 degrees C respectively.