Solid oxide cell fuel electrodes based on perovskite oxides are desirable to avoid problems with Ni-based anodes, including coking in hydrocarbon fuels and degradation due to fuel impurities or redox cycling. However, oxide anode electrochemical performance is often lacking, limited by surface processes such as the dissociative adsorption of hydrogen. One way to improve such anodes is by the addition of a reducible cation in the oxide formulation, resulting in cation exsolution and nucleation of metallic nanoparticles on oxide surfaces during cell startup and operation. For example, substitution of small amounts of Ni or Ru on the B-site of Sr(Ti,Fe)O₃ results in the formation of Ni-Fe or Ru-Fe nanoparticles, respectively, during exposure of the electrode to fuel during cell operation. This talk will examine the microstructural evolution of these exsolution anodes, making use of in situ x-ray diffraction measurements to detect formation of exsolved metal alloys and oxide phase changes. Exsolved metal nanoparticles enhance electrochemical performance, usually by promoting hydrogen dissociation on electrode surfaces. Changes in perovskite stoichiometry resulting from B-site exsolution can also impact the phase stability of the oxide, in some cases resulting in the formation of Ruddlesden-Popper phases that deleteriously affect electrochemical performance. The application of exsolution in fuel electrodes in novel thin-electrolyte oxygen-electrode-supported cells is discussed; the results indicate that performance in H₂/H₂O fuel is superior to Ni-YSZ in both electrolysis and fuel cell modes. Electrochemical characteristics of the exsolution electrodes are especially superior to Ni-YSZ when operated in CO/CO₂ fuel.