CeXO2 (X: Fe, Mn) nanoparticles, synthesized using the coprecipitation route, were investigated for their structural, morphological, magnetic, and electrochemical properties using X-ray diffraction (XRD), field emission transmission electron microscopy (FE-TEM), dc magnetization, and cyclic voltammetry methods. The single-phase formation of CeO2 nanoparticles with FCC fluorite structure was confirmed by the Rietveld refinement, indicating the successful incorporation of Fe and Mn in the CeO2 matrix with the reduced dimensions and band gap values. The Raman analysis supported the lowest band gap of Fe-doped CeO2 on account of oxygen non-stoichiometry. The samples exhibited weak room temperature ferromagnetism, which was found to be enhanced in the Fe doped CeO2. The NEXAFS analysis supported the results by revealing the oxidation state of Fe to be Fe2+/Fe3+ in Fe-doped CeO2 nanoparticles. Further, the room temperature electrochemical performance of CeXO2 (X: Fe, Mn) nanoparticles was measured with a scan rate of 10 mV s−1 using 1 M KCL electrolyte, which showed that the Ce0.95Fe0.05O2 electrode revealed excellent performance with a specific capacitance of 945 Fּ·g−1 for the application in energy storage devices.