We present combined Synchrotron X-ray Absorption Near Edge Spectroscopy (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) study of La0.4Sr0.6Ti1-yCoyO3 +/-delta (0 <= y <= 0.5), which are promising electrode materials for symmetric solid oxide fuel cells. The measurements were performed at room temperature at the Ti and the Co K-edges in order to determine the local structural and electronic changes around the two transition metals. We find that Ti remains in a higher formal valence (around 4+) independent of the Co concentration. In contrast to this, dramatic and systematic changes are observed for the Co as a function of y. We conclude that the stability of the Ti4+ triggers the A-site deficiency in our samples and predicts that oxygen vacancies are much more easily formed at large Co content, which in turn will greatly enhance the performance as electrode material. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.