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The active oxygen species on the surface of additive/rare earth oxides (RE2O3)catalysts have been investigated by means of XPS, O2-TPD and XRD. The results indicate that there exist O and O2- species on the surface of the catalysts at low temperature. The performance of the catalyst is dependent on the concentration of O species on the catalyst surface. It is suggested that the O- species formed from O species at high temperature is active oxygen species for OCM reaction.