The entire world’s challenge is to find out the renewable energy sources due to rapid depletion of fossil fuels because of their high consumption. Solid oxide fuel cells (SOFCs) are believed to be the best alternative source, which converts chemical energy into electricity without combustion. Nanostructure study is required to develop highly ionic conductive electrolytes for SOFCs. In this work, the calcium doped ceria $(Ce0.8Ca0.2O1.9)$ coated with 20% molar ratio of two alkali carbonates (CDC-M: $MCO3$, where $M=Na$ and K) electrolyte was prepared by coprecipitation method. Ni based electrode was used to fabricate the cell by dry pressing technique. The crystal structure and surface morphology were characterized by an X-ray diffractometer, scanning electron microscopy (SEM), and high resolution transmission electron microscopy (TEM). The particle size was calculated in the range 10–20 nm by Scherer’s formula and compared with SEM and TEM results. The ionic conductivity was measured by using ac electrochemical impedance spectroscopy method. The activation energy was also evaluated. The performance of the cell was measured $0.567W/cm2$ at temperature $550°C$ with hydrogen as a fuel.