Defect passivation using oxygen has been identified as an efficient and convenient approach to suppress nonradiative recombination and improve the photovoltaic performance of hybrid organic inorganic halide perovskites (HHPs). However, oxygen can seriously undermine the chemical stability of HHPs due to the reaction of superoxide with protonated organic cations such as CH3NH3+ and [(NH2)(2)CH](+), thus hindering the deep understanding of how oxygen affects their defect properties. Here we substitute free-proton inorganic Cs+ for organic moiety to avoid the negative effect of oxygen and then systematically investigate the oxygen passivation mechanism in all-inorganic halide perovskites (IHPs) from theory to experiment. We find that, in contrast to conventional oxygen molecule passivation just through physisorption on the surface of perovskites, the oxygen atom can provide a better passivation effect due to its stronger interaction with perovskites. The key point to achieve O-passivated perovskites rather than O-2 is the dry-air processing condition, which can dissociate the O-2 into O during the annealing process. O-passivated IHP solar cells exhibit enhanced power conversion efficiency (PCE) and better air stability than O-2-passivated cells. These results not only provide deep insights into the passivation effect of oxygen on perovskites but also demonstrate the great potential of IHPs for high photovoltaic performance with simplified ambient processing.