The interaction of highly pure polycrystalline silver samples with ozone (500 ppb) was investigated under certain relative humidity (RH) content (0%, 50% and 90%) in synthetic air. All experiments were performed at room temperature (22 °C) and atmospheric pressure. Highly surface sensitive methods were used to investigate chemical, morphological and structural changes and composition of the corrosion products formed at different RH and reaction times. Silver is oxidized by ozone forming Ag₂O/AgO(Ag^IAg^IIIO₂) surface species. The oxide formation and corrosion rate is dependent on the RH content in the atmosphere, showing that silver is most susceptible to ozone oxidation at 50% RH.