In-situ X-ray absorption near-edge structure (XANES) experiments were performed on a working reformate-air fuel cell to study the structure of carbon supported Pt-Ru anode electro-catalyst. The fuel cell was operated in a normal mode without the use of supplemental electrolytes. A fresh membrane electrode assembly (MEA) and a conditioned MEA were studied at different operating conditions of the fuel cell and different feud (pure H-2 or H-2/CO [100 ppm CO]) at the anode. The in-situ Pt L-III-edge and Ru K-edge XANES of the fuel cell MEAs showed metallic characteristics under all operating conditions. These results demonstrate that, under the reducing conditions of normal fuel cell operation, the Pt-Ru catalyst exists as a metallic phase(s).