The world’s present reserves in terms of fossil fuels are exhausting speedily. Such rapid energy consumption can be caused of unsustainable worldwide progress. Therefore, the researcher’s challenge is to identify the most efficient and economical energy conversion method to provide a viable replacement for the ongoing conventional energy converters. In this context, fuel cell technology (solid oxide fuel cells (SOFCs)) can play a key role and convert hydrocarbon energy into electrical energy. The conventional electrolyte YSZ based SOFCs work at high temperature ∼1000 °C. In this present research, the new ceramics electrolytes materials boron doped ceria (BDC) have been developed by auto-combustion technique. The prepared materials have been characterized by X-ray diffraction (XRD) and TEM. The crystallite sizes of all prepared samples are in the range of 50–80 nm applying Scherer’s formula. The electrical studies and fuel cell performance have been completed at temperature ≤ 700 °C. The doping of boron into ceria has significantly improved the electrical conduction of pure ceria oxide which has been studied using four-probe setup. The maximum ionic conductivity and power density of B0.20:Ce0.80 (molar ratio) electrolyte material named as E4 have been achieved and found to be 0.09 S/cm at 700 °C and 198.125 mW/cm2 at 650 °C. It has been observed that all electrochemical results are consistent with the doping of boron into ceria.