The synthesized catalytic systems are well characterized by X-Ray Diffraction technique, Electron microscopy (TEM &SEM), Raman spectral study, FTIR spectroscopy, UV-DR Spectra and BET surface area analysis. Among the prepared catalysts, copper oxide modified ceria system is found to be the most effective for the mineralization of methylene blue. It is concluded that oxygen vacancies and Ce3+ ions in the catalyst have prominent role in deciding the performance of M/CeO2 catalysts in Fenton-like oxidation reactions. Besides this, the decisive role of redox potential of the doped metal ions on the efficiency of nanoceria in Fenton-like oxidation has also been examined for the first time in literature. A correlation between redox potential of doped metal ions and the oxidation activity is also established.