In this study the surface properties of LSCF have been studied in in-situ from room temperature to 1000oC using a High Temperature Environmental Scanning Electron Microscope (HT-ESEM) under a number of different atmospheres. Dense, polished La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) was observed during thermal annealing under a vacuum, pure oxygen, pure water and humid air atmospheres. The effect each atmosphere had on the surface morphology has been characterized in real time and analysed chemically using EDX. Significant differences in the surface behaviour were seen under each atmosphere. The results observed in the HT-ESEM were complimentary to in-operando surface exchange measurements and have enabled a more detailed understanding of SOFC cathode decomposition.