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The leaching of the spent fuel matrix (UO2) is function of the radiolytic products formation. The effect of each radioiytic product on the leaching process is not totally understood. In the literature, the influence of H2O2 on the dissolution process is described from the qualitative point of view, and most of the studies were performed for pH values from 8 to 12. In this paper we report on the effect of the H2O2 in the leaching process of UO2 by dissolution experiments at various H2O2 concentrations. Also, it was tested the influence of S/V ratio (surface area exposed to the leaching media) on the UO2 leaching and secondary phases formation. It was identified the formation of secondary phases on the UO2 surface. Solid phases characterization was carried out by x-ray Photoelectron Spectrometry (XPS), x-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) techniques. By XPS studies the secondary phase formed corresponded to a U(VI) phase. By XRD analyses the solid was identified as studtite, UO4 - 4H2O, (card n0 16–206, [I]). A comparison of the U(VI) phases formed in spent fuel and UO, leaching experiments in various media has been carried out.