Growth of magnetron sputtered Pt/CeO 2 thin films on Si and Si 3 N 4 were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Interaction of Pt/CeO 2 films with Si on Si and Si 3 N 4 substrates was extensively investigated by XPS. XRD studies show that films are oriented preferentially to (200) direction of CeO 2 . XPS results show that Pt is mainly present in +2 oxidation state in Pt/CeO 2 /Si film, whereas Pt 4+ predominates in Pt/CeO 2 /Si 3 N 4 film. Concentration of Pt 4+ species is more than four times on Si 3 N 4 substrate as compared with that on Si. Ce is present as both +4 and +3 oxidation states in Pt/CeO 2 films deposited on Si and Si 3 N 4 substrates, but concentration of Ce 3+ species is more in Pt/CeO 2 /Si film. Interfacial reaction between CeO 2 and Si substrate is controlled in the presence of Pt. Pt/Ce concentration ratio decreases in Pt/CeO 2 /Si 3 N 4 film upon successive sputtering, whereas this ratio decreases initially and then increases in Pt/CeO 2 /Si film.