In this study, the effect of the temperature on the surface segregation and Cr deposition on La0.6Sr0.4Co0.2Fe0.8O3-ä (LSCF) cathodes is investigated using confocal laser Raman spectroscopy and electrical conductivity relaxation (ECR) method. The results show that the segregation of SrO phase on the LSCF surface decreases with the decreasing of temperature. Cr deposition takes place on the LSCF surface after the heat-treatment in the presence of Cr2O3 at temperature range of 700 to 900°C for 48h, forming SrCrO4 phase. As the temperature decreases, less SrCrO4 phase is detected. The surface exchange coefficient of LSCF measured at 900, 800 and 700°C after the heat-treatment in the presence of Cr2O3 for 48h is 1.5×10−4, 1×10−4 and 4×10−5cm s−1, respectively, which is much lower than that measured on the sample tested in the absence of Cr deposition. Chromium poisoning deteriorates the surface exchange and diffusion processes for the O2 reduction reaction on LSCF electrodes. Cr deposition decreases significantly with the decrease of temperature, most likely due to the reduced Sr segregation as well as the decrease of the partial pressure of gaseous Cr species at reduced temperatures.