The demand for clean, secure, and sustainable energy sources has stimulated great interest in fuel cells. Among various types of fuel cells, solid oxide fuel cells (SOFCs) represent the cleanest, most efficient and versatile chemical-to-electrical energy conversion system. Here we report our recent progress in modeling, simulation, and in situ characterization of electrode processes in SOFCs, including quantum chemical modeling of the interactions between O-2 and cathode materials as well as those between anodes and fuel molecules with contaminants, continuum modeling of charge and mass transport along surfaces and across interfaces, and characterization of surface species, interfacial processes, and new phases using in situ Raman spectroscopy.