Nanostructured perovskite materials doped with transition metal ions have attracted significant attention due to their unique electronic and dielectric properties. In this study, we present the synthesis and thorough characterization of cobalt (Co) and nickel (Ni) ion-doped CeMnO3 (CMO) perovskite nanoparticles using a modified polyacrylamide gel method. Our structural analysis suggests that the perovskite phase stabilizes with an orthorhombic phase (Pbnm space group). Morphological analysis conducted via field emission scanning electron microscopy (FESEM) unveils the formation of clustered nanospherical particles. X-ray photoelectron spectroscopy (XPS) reveals mixed oxidation states of Ce, Mn, and Ni ions. Furthermore, UV–Vis and photoluminescence spectra analyses demonstrate a distinctive reduction in band gap and suppressed charge carrier recombination upon doping. The substitution of Ni and Co ions also enhances the screening effect, reducing Coulombic interaction between photoexcited electrons and holes and subsequently increasing the dielectric constant. Analysis of the Cole-Cole plot demonstrates the augmentation of capacitance with Ni substitution. These findings collectively suggest that the decreased dielectric loss and enhanced dielectric constant support the feasibility of these materials for application in storage devices.