Periodic spin-polarized hybrid density functional theory calculations have been performed to investigate the reactivity of pristine, O-defective, and Ag-decorated CeO 2 (111) and TiO 2 (110) surfaces with a small Ag 10 cluster toward O 2 . The adsorption of O 2 and its subsequent dissociation have been studied in order to provide a better understanding of the role of the oxide, the metallic nanoparticle, and their interaction in the reactivity of composite metal/metal oxide materials toward O 2 , as potential catalysts to this reaction. Structural, energetic, electronic, and vibrational properties of all species involved in the different reaction paths considered have been fully characterized. On the stoichiometric surfaces, Ag 10 is oxidized and reduces surface Ce 4+ / Ti 4+ ions, while on the O-defective surfaces, the adhesion of silver is promoted only on CeO 2 but unfavored on TiO 2 . On the other hand, on the silver-free supports, O 2 strongly adsorbs at vacancies and preferentially reduces to peroxide. When no O vacancies are considered on the Ag 10 -decorated supports, the net positive charge on Ag 10 actually prevents the adsorption and reduction of O 2 . Instead, when O vacancies are included, two reaction pathways are observed; oxygen molecules can weakly absorb on the silver cluster as a superoxide moiety or strongly adsorb at the vacancy as peroxide. The dissociation of the O−O bond of the peroxide is favored both from the thermodynamic and kinetic points of view in silver-decorated surfaces, in contrast with the silver-free cases. In addition, Ag 10 /CeO 2 shows higher activity toward the O 2 adsorption and dissociation than Ag 10 /TiO 2 , which can be related both to the higher ionicity and superior electron storage/release ability of ceria with respect to titania, thus leading to the weakening of the O−O bond and providing lower activation barriers for oxygen reduction. These results deepen the current understanding of the reactivity of metal/metal oxide composites toward O 2 , especially elucidating how the surface stoichiometry affects the charge state of the metal clusters, and hence the reactivity of these interfaces toward O 2 , with potential important consequences when such composites are considered for catalytic applications.