Pt/Ru catalysts with two very different structures were examined with X-ray absorption near edge structure (XANES). One sample was an industrial methanol fuel cell Pt/Ru alloy catalyst black, and the second was a carbon-supported Pt/Ru catalyst. In both cases the as-prepared Pt/Ru catalysts were found, with XANES, to be predominately in the form of Pt and Ru oxides. When these catalysts were placed in an electrochemical cell and held in the potential region where methanol oxidation occurs, XANES data indicate that the metal oxides were reduced to the metallic form. These results also demonstrate that conclusions about the electrocatalytic activity of Pt/Ru materials for methanol oxidation drawn from the characterization of as-prepared samples have little relevance.