In order to better understand the mechanism of the reaction of oxygen reduction at the surface of strontium doped lanthanum manganites (LSM) cathodes in solid electrolyte fuel cells (SOFC), the surface properties of La0.8Sr0.2MnO3 powders and screen-printed layers have been characterised by various techniques. Strontium enrichment at the surface has been evidenced by X-ray photoelectron spectroscopy according to the conditions of annealing (temperature, oxygen pressure) and polarisation treatments of the samples. The interaction between oxygen and La0.8Sr0.2MnO3 for SOFC cathodes has been studied by thermo-programmed desorption, in situ infrared spectrometry and calorimetry. The results indicate that various adsorbed oxygen species may exist on the surface of LSM depending on temperature. The presence of various adsorbed oxygen species and the surface Sr segregation are important factors to consider in the mechanism of oxygen reduction at LSM SOFC cathodes since they could be responsible for many discrepancies between the interpretations that can be found in the literature data. (c) 2006 Elsevier B.V. All rights reserved.