In recent years, more research interest is growing in energy conversion, especially low-temperature ceramic fuel cells (LT-CFCs). Moreover, fast ionic conduction through surface doping is a favorite subject in CFCs. Also, it indicates a promising and stable strategy to optimize ions in the developed electrolytes for LT-CFCs. In this regard, herein, we have designed LaSrTCrCeO3 (LSTCrCe) synthesized using the sol−gel technique to be used as an electrolyte for LT-CFCs. The prepared electrolyte LSTCrCe was used as an electrolyte sandwiched between symmetrical electrodes and delivered stunning fuel cell performance (1031 mW/cm2 ) with better stability at the low operating temperature of 520 °C. The low grain boundary resistance manifests the high ionic conduction + microstructural properties of LSTCrCe, assisting with higher fuel cell performance. The doping enables the Fermi level to alternate the position which further establishes a space charge region constituting a built-in electric field, helping to enhance the ion transportation through the surface and interface. This work thus points out a specific type of electrolyte with different working mechanisms from previous studies. It indicates a feasible approach to develop highperforming and stable electrolytes for LT-CFCs.