The presence of both chromium and sulfur (Cr/S) contaminants on the microstructure and electrocatalytic activity properties of La0.6Sr0.4Co0.2Fe0.8O3-delta (LSCF) electrodes of solid oxide fuel cells (SOFCs) is studied, using Confocal laser Raman spectroscopy, XRD, scanning electron microscopy, X-ray photoelectron spectroscopy (XPS) and electrical conductivity relaxation (ECR) methods. LSCF dense bar samples were heat treated in the presence of Cr2O3 and 20 ppm SO2 and in the temperature range of 600-900 degrees C. The deposition and reaction products between LSCF and Cr/S depend on the temperature: SrCrO4 only forms on LSCF samples at 900 degrees C and 800 degrees C, while formation of SrSO4 phase occurs at all temperatures studied. The results indicate that sulfur shows a higher activity with LSCF, as compared to gaseous Cr species. Segregated SrO is more likely to react with gaseous Cr species at higher temperatures, however, reaction with SO2 is more pronounced at lower temperatures, forming SrSO4. ECR results indicate that co-deposition of Cr and sulfur significantly deteriorates the surface exchange and diffusion processes for the O-2 reduction reaction on LSCF electrodes. (C) The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-ncU4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: [email protected]. All rights reserved.