We will briefly review in situ synchrotron x-ray investigation of model thin film cathode systems for solid oxide fuel cells. The film cathodes examined in this study are (La,Sr)MnO3_δ (LSM), (La,Sr)CoO3_δ (LSC), and La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) thin films epitaxially grown on YSZ single crystal substrates by the pulse laser deposition technique. We find in all cases that Sr is enriched or segregated to the surface of the film cathodes. We concluded that the Sr enrichments or segregations are mainly the results of annealing because they do not depend on whether the cathodes are electrochemically biased or not during annealing. However, at least in the case of LSCF, we find that B-site Co segregates rather uniformly to the surface and the segregation responds sensitively and reversibly to the electrochemical bias.