This report demonstrates the synergistic enhancement in intrinsic electrochemical performance of a novel nanocomposite, copper oxide/barium oxide (CuO/BaO), for supercapacitor applications. The CuO/BaO nanocomposite was synthesized via a simple one-step wet chemical route. Its crystalline structure, surface morphological features, compositional confirmation, and particle size distribution were examined using powder XRD, SEM, EDAX, elemental mapping, TEM, and SAED pattern analyses. Electrochemical measurements were performed in a three-electrode system using 3 M KOH electrolyte, with the CuO/BaO nanocomposite coated on Ni foam as the working electrode. Cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) studies evidenced an enhanced electrochemical performance of the synthesized nanocomposite over its counterparts. Electrochemical impedance spectroscopy (EIS) confirmed reduced internal and charge transfer resistances, indicating enhanced conductivity. GCD-derived specific capacitance of the CuO/BaO nanocomposite was found to be 1392.2 F/g at a current density of 0.6 A/g. Owing to its high-specific capacitance, simple synthesis procedure, and cost-effectiveness, the CuO/BaO nanocomposite is proposed as a promising electrode material for supercapacitor applications.