Supercapacitors based on mixed metal oxides are being developed as potential devices for large-scale energy storage applications with physical flexibility, thanks to their low cost and good electrochemical performance. This work demonstrates a novel approach to enhancing the electrochemical performance of bismuth–cerium oxide BiCeO₃ (BC) through thiourea doping. The incorporation of sulfur, confirmed by EDS, induced significant structural modifications, including a reduction in crystallite size from 42.5 nm to 34.8 nm and the emergence of new diffraction planes (002) and (222) in XRD patterns. These changes, indicative of successful lattice doping, yielded a more nanostructured morphology with increased active surface area and a 20% reduction in the optical band gap. Electrochemically, the thiourea-doped BiCeO₃ (BCT) electrode delivered a marked improvement, exhibiting a specific capacitance of 150 F·g⁻¹ at 25 mV·s⁻¹, a 17.2% increase over the pure BiCeO₃ (128 F·g⁻¹). Furthermore, BCT demonstrated superior rate capability and a 43% reduction in overall impedance, underscoring enhanced charge transfer kinetics and ionic conductivity. The synergy between sulfur-induced structural defects, increased electroactive surface area, and improved electronic structure establishes thiourea doping as an effective strategy for developing high-performance BiCeO₃-based supercapacitors.