In this study, a novel Co3O4/CeO2 nanocomposite for supercapacitors was fabricated through a one-step hydrothermal method, to achieve distinct crystalline phases and a unique flower-like structure. Integrated into a binder-free electrode (BFE) on Ni foam, the Co3O4/CeO2@NF electrode outperformed individual Co3O4 and CeO2-based electrodes. The synergistic effect between Co3O4 and CeO2, enhances the overall surface area, porosity and conductivity of the composites, which improved the supercapacitor characteristics. Detailed analyses confirmed the Co3O4/CeO2@NF electrode's superior cyclic voltammetry, galvanostatic charge-discharge, rate capability, and stability under potassium hydroxide (KOH) and redox additive electrolytes (RAE). The incorporation of RAE further boosted the performance, showcasing the potential for advanced energy storage applications. The assembled asymmetric supercapacitor (ASC) device exhibited outstanding energy and power densities, making it promising for practical applications. Comprehensive electrochemical impedance spectroscopy (EIS) studies offered insights into charge transfer dynamics, highlighted the positive impact of redox additives. This work contributed to understand the synergistic effects in metal oxide composites on advancing the high-performance supercapacitor development.