Sulfur in the air stream is one of the major contaminants affecting the performance stability of cathodes of solid oxide fuel cells (SOFCs) such as La0.6Sr0.4Co0.2Fe0.8O3-delta (LSCF) perovskite. Here sulfur deposition and poisoning was investigated on LSCF bar samples in the presence of 20 ppm SO2 and temperature range of 400-900 degrees C, using scanning electron microscopy, confocal laser Raman spectroscopy and electrical conductivity relaxation (ECR) methods. Sulfur (SO2) reacts with LSCF, primarily forming SrSO4 at high temperatures (i.e., >= 700 degrees C) and SrS at low temperatures (i.e. <700 degrees C). Surface segregated SrO plays an important role in the sulfur deposition. The most important observation of this study is that sulfur deposition shows a distinct volcano-type dependency on the heat-treatment temperature and is most pronounced at temperatures around 700 degrees C, indicating that the reaction rate between the segregated SrO and SO2 is highest at similar to 700 degrees C. The ECR results indicate that the surface exchange coefficient of LSCF after the exposure to 20 ppm SO2 at 700, 800 and 900 degrees C for 48 h is two orders of magnitude lower than that of the sample tested in the absence of SO2, indicating that sulfur poisoning deteriorates significantly the surface exchange and diffusion processes for the O-2 reduction reaction on LSCF electrodes. (C) 2014 The Electrochemical Society. All rights reserved.