Pt/C, PtRu/C and PtMo/C electro catalysts were prepared in different compositions by incipient wetness impregnation method. These catalysts were characterized by X-ray diffraction (XRD) and X-ray absorption near-edge structure (XANES) to understand the miscibility into solid solution and to calculate the d-orbital vacancy, respectively. Pt with Ru and Mo forms a single alloy which was confirmed by XRD date. XANES was measured at Pt L-II and L-III edges and K edges of Ru and Mo to determine the oxidation states of these metals in different compositions. Further calculations of d-orbital vacancy of Pt revealed more information that increasing the Ru or Mo content increases d-orbital vacancy. As Mo oxidizes faster than Ru, magnitude of d-orbital vacancy is high in the case of Ru compared to Mo. In situ XENES study was also conducted in methanol fuel cell to understand the oxidation states and methanol oxidation mechanism. (c) 2005 Published by Elsevier B.V.