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Ce[Formula: see text]Pr[Formula: see text]O2 ([Formula: see text], 0.02, 0.04, 0.06, and 0.08) nano-materials synthesized using co-precipitation method have been investigated mainly for electronic structure properties in this manuscript. Findings and supporting studies are presented to understand the role of valence states of host and dopant cations information of F[Formula: see text] centers through X-ray photoelectron spectroscopy (XPS). Sustained cubic fluorite system confirmed by X-ray diffraction (XRD) analysis and red-shifting of energy gap by UV–Vis spectroscopy in all the samples are our findings. Samples further implored by XPS indicate incidence of cerium and Pr cations in both the oxidation states of 4[Formula: see text] and 3[Formula: see text] , respectively. Finally, it has been observed that optical, electronic structure and magnetic properties of CeO2 nanomaterials can be modified by Pr-doping, promising better yield samples with good amount of ferromagnetism for potential uses in the technological applications like spintronics, optoelectronics, and photocatalytic.