AbstractThe surface oxygen exchange on oxides with high oxygen ion mobility is modelled with a two step reaction with adsorbed mono-atomic oxygen species as intermediate. Interpretation of the Po2 dependence of the exchange rates, following from this model, indicates that these adsorbed oxygen atoms are singly charged.For the stabilized δ-Bi2O3 solid electrolyte a good agreement has been found between the isotope exchange model and the electrochemical study of the oxygen exchange using gold electrodes. For the mixed La-Sr cobaltite perovskite a change in the surface exchange reaction is observed going from room temperature to 600°C. Indications are that above 450°C the bulk exchange is rate limiting with a (Po2)−1 dependence while below this temperature it is assumed that the dissociative adsorption is rate limiting with a (Po2)1/2 dependence.