The reactivity of atomically dispersed Pt(2+) species on the surface of nanostructured CeO2 films and the mechanism of H2 activation on these sites have been investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy in combination with density functional calculations. Isolated Pt(2+) sites are found to be inactive towards H2 dissociation due to high activation energy required for H-H bond scission. Trace amounts of metallic Pt are necessary to initiate H2 dissociation on Pt-CeO2 films. H2 dissociation triggers the reduction of Ce(4+) cations which, in turn, is coupled with the reduction of Pt(2+) species. The mechanism of Pt(2+) reduction involves reverse oxygen spillover and formation of oxygen vacancies on Pt-CeO2 films. Our calculations suggest the existence of a threshold concentration of oxygen vacancies associated with the onset of Pt(2+) reduction.