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Pure and Co doped CeO₂ nanostructures were synthesized with different weight percentages of Co (0–7 wt%) via microwave technique. The thermal, structural, optical and morphological studies of the prepared nanoparticles were undertaken by thermo gravimetry (TG), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), photoluminescence (PL), Raman and scanning electron microscopy (SEM & EDS). Electrochemical studies reveal that the Co(5%)-CeO₂ (Co-C5) electrode exhibits better electrochemical storage. Co-C5 electrode exhibits a maximum specific capacitance of 573 F g⁻¹ at a current density of 2 A g⁻¹. The stability of the electrode was tested and it exhibits 96% of cyclic stability even after 1000 continuous charge-discharge cycles and the obtained results are discussed in detail.