<p>Supercapacitors demand materials with rapid charge/discharge, high power, and long lifespan, where transition-metal oxides like V₂O₅ excel due to tuneable redox activity. Pure and Ce-doped (3, 5, 7 wt.%) V₂O₅ nanoparticles are synthesised by co-precipitation method; 3% Ce-doped V₂O₅ nanoparticles exhibit enhanced electrochemical performance. Comprehensive characterization confirms orthorhombic phase purity (XRD, JCPDS 01–001-0359), layered vibrational modes (FTIR), morphology (FE-SEM), and bandgap narrowing (UV–Vis). XPS reveals Ce³⁺/Ce⁴⁺ coexistence, inducing oxygen vacancies. Ce doping significantly boosts BET surface area from 50.45 m²&#xa0;g⁻¹ for V₂O₅ to 81.42 m²&#xa0;g⁻¹ for 3% Ce-doped V₂O₅ and also increases the pore volume from 0.21 cm³&#xa0;g⁻¹ for V₂O₅ to 0.35 cm³&#xa0;g⁻¹¹ for 3% Ce-doped V₂O₅ with type IV isotherms and H3 hysteresis confirming preserved mesoporous hierarchical porosity. 3% Ce-doped V₂O₅ optimally enhances conductivity and stability via Ce⁴⁺/V⁵⁺. HRTEM patterns confirm polycrystallinity, ideal for high surface area and exhibit high specific capacitance. Supercapacitor testing yields maximum specific capacitances of 375.93 F g⁻¹ for pure V₂O₅ and 526.31 F g⁻¹ for 3% Ce-doped V₂O₅ at 0.5&#xa0;mV&#xa0;s⁻¹, with 92% retention over 1000 cycles. These findings position 3% Ce-doped V₂O₅ nanoparticles as a promising electrode for high-performance energy storage.</p>