The evolution of the Mn charge state, chemical composition, and electronic structure of La0.8Sr0.2MnO3 (LSMO) cathodes during the catalytic activation of solid oxide fuel cell (SOFC) has been studies using X-ray spectroscopy of as-processed, exposed, and activated dense thin LSMO films. Comparison of O K-edge and Mn L-3,L-2-edge X-ray absorption spectra from the different stages of LSMO cathodes revealed that the largest change after the activation occurred in the Mn charge state with little change in the oxygen environment. Core-level X-ray photoemission spectroscopy and Mn L-3 resonant photoemission spectroscopy studies of exposed and as-processed LSMO determined that the SOFC environment (800 degrees C ambient pressure of O-2) alone results in La deficiency (severest near the surface with Sr doping > 0.55) and a stronger Mn4+ contribution, leading to the increased insulating character of the cathode prior to activation. Meanwhile, O K-edge X-ray absorption measurements support Sr/La enrichment nearer the surface, along with the formation of mixed SrxMnyOz and/or passive MnOx and SrO species. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3519075] All rights reserved.