The composite of ceria has been widely studied as an electrode material for supercapacitors applications due to its high energy density. Herein, we synthesize CeO2/NiO nanocomposite via a hydrothermal route and explore its different aspects using various characterization techniques. The crystal structure is investigated using X-ray diffraction, Fourier transform infrared, and Raman spectroscopy. The formation of nanoflakes which combine to form flower-like morphology is observed from scanning electron microscope images. Selected area scans confirm the presence of all elements in accordance with their stoichiometric amount and thus authenticate the elemental purity. Polycrystalline nature with crystallite size 8–10 nm having truncated octahedron shape is confirmed from tunneling electron microscope images. Using X-ray photoelectron spectroscopy the different oxidation states of Ce and Ni are observed which play the role of active sites in the electrochemical performance of this nanocomposite material. Cyclic Voltammetry(CV) measurements at different scan rates and Galvanic Charge Discharge (GCD) measurements at different current densities are performed to probe the electrochemical response which revealed the potential of CeO2/NiO nanocomposite as an electrode material for energy storage devices.