We present synchrotron x-ray investigations of thin film La0.6Sr0.4Co0.2Fe0.8O3 - (delta) (LSCF) model cathodes for solid oxide fuel cells, grown on electrolyte substrates by pulse laser deposition, in situ during half-cell operations. We observed dynamic segregations of cations, such as Sr and Co, on the surfaces of the film cathodes. The effects of temperature, applied potentials, and capping layers on the segregations were investigated using a surface sensitive technique of total external reflection x-ray fluorescence. We also studied patterned thin film LSCF cathodes using high-resolution micro-beam diffraction-measurements. We find chemical expansion decreases for narrow stripes. This suggests the expansion is dominated by the bulk pathway reactions. The chemical expansion vs. the distance from the electrode contact was measured at three temperatures and an oxygen vacancy activation energy was estimated to be 1.4 eV.