The rapid growth of portable electronics and electric vehicles has intensified the global demand for high-performance energy storage devices with superior power density, energy density, and long cycle life. Among transition metal oxide-based electrode materials with potential for energy storage, we report the development of MnO2–V2O5 nanocomposite electrodes for supercapacitor applications. Pure MnO2 and V2O5 were successfully fabricated via a simple and economical sol–gel method, while (MnO2)x–(V2O5)1−x (x = 1, 0.75, 0.50, and 0) nanocomposites were fabricated through an ex situ method. Analytical techniques, including X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and UV-visible spectroscopy, were employed to investigate the structural, morphological, and optical properties of the electrodes. Furthermore, the electrochemical properties were systematically analysed using cyclic voltammetry, galvanostatic charge–discharge measurements, and electrochemical impedance spectroscopy. The (MnO2)0.75–(V2O5)0.25 nanocomposite demonstrated a remarkable specific capacitance of 666 F/g at a current density of 0.5 A/g in 1 M KOH electrolyte. Additionally, the electrode material exhibited an energy density of 23 Wh/kg and a power density of 450 W/kg, while maintaining a capacitance retention of 95% after 1,500 cycles. The incorporation of V2O5 boosted the conductivity and significantly optimised the number of lattice defects. This work substantially reinforces the importance of metal oxide-based nanocomposites for future energy storage devices.