Researchers are being focused on designing sustainable and renewable energy storage systems, especially electronically tuned energy storage devices, due to increased electricity demand and fossil fuel depletion. Batteries and supercapacitors have substantially improved energy storage in recent years. In the course of developing nanomaterials with sustainable dual functionality, this study reviews the synthetic and dual applications of cerium-enriched copper oxide monodispersed nanomaterials, especially their synergic photocatalysis, which is much better than their superior supercapacitor storage. The sol-gel method was used for the preparation of nanoarchitectures, in which the crystalline structure and morphology were studied using X-Ray diffraction spectroscopy (XRD) and Scanning electron microscope (SEM) techniques. An important fact is that the nanoarchitectures with 10% cerium showed their crystallite size, which was reported to be 17.30 nm, implying accuracy in the synthesis. The results of SEM indicate single-phase particles with slight agglomeration. The corresponding 10% CeO2@CuO nanostructures were then comprehensively evaluated for both photocatalytic activities and energy storage purposes. In relation to photocatalysis, nanoarchitectures proved to be efficient for Rhodamine B (RhB) dye with 92% degradation after 200 min. of the reaction time. Moreover, the synthesized nanoparticles demonstrated excellent supercapacitor performance. The tailor-synthesized nanoarchitectures had a specific capacitance of 875 F/g and energy density achieved 78 Wh/g, which clearly shows the prospect for such materials used in high-energy storage devices. The10% CeO2@CuO nanoarchitecture retained 88% of capacitance for 2000 cycles, which made it possible to demonstrate the good robustness and durability of the materials for long-term utilization in energy storage. These findings contribute to the field of nanoscience and nanotechnology, offering a hopeful channel for the future development of advanced materials that have dual functionality.