High surface area polycrystalline calcium oxide forms ozonide O-3(-) ions upon O-2 adsorption and NO32- anions under low pressures of NO. Both radical anions, detected by electron paramagnetic resonance (EPR), are not observed in the case of the homologous magnesium oxide. This behavior reveals the presence, in CaO, of anomalies with respect to the ideal composition of an ionic oxide which are identified in terms of two main types of defects. The first type consists of positive holes dispersed in the bulk and originated by the unavoidable presence of Na+ ions in the composition of the solid. The decomposition of the surface ozonide shows the formation of a transient surface stabilized O- ( the chemical notation of a positive hole associated to an oxide ion) which is for the first time reported at the surface of CaO. The second type of defect consists of surface peroxide groups ( present at particular surface sites where they are formed by pairing of two distinct O-) which react with nitric oxide (NO) yielding NO32- radical anions. The presence of peroxide is not related to the presence of impurities but, rather, to a certain propensity of the solid to form such ions at the surface along the dehydration process.