We report here on the development of a novel type of solid oxide fuel cell anodes that are based on Mn containing perovskites and prepared by infiltration of electrode precursor solutions into yttria stabilized zirconia scaffolds. The presence of Mn, even in small amount, on the B-site of the ABO₃ structure leads to electrode microstructures that offer a large surface area that is available for electrochemical reactions. The oxides form a remarkable thin coating on the electrode scaffold after high temperature sintering. The evolution of those films in reducing environments creates arrays of interconnected ̃10nm scale particles covering the electrode scaffold. Such electrodes, based on LSCM with small amounts of added catalyst, provide outstanding performance, both for the direct oxidation of methane in solid oxide fuel cells, and the reduction of pure CO₂ in solid oxide electrolyzers.