The transition metal alloy electro-catalysts were evaluated as low cost alternatives to direct oxidation of methanol fuel cells (DMFCs) and compared with the generally accepted noble metal and alloy catalysts using cyclic voltammetry and X-ray absorption spectroscopy techniques. The effect of methanol concentration in sulfuric acid, temperature, and catalyst surface area were evaluated and matched with the proper electro-oxidation mechanisms. The alloy catalyst Pt-Co/C was found to be a better catalyst for methanol oxidation in acid solution compared with other transition metal alloys. The observed current oscillations in Pt-Cu/C in low and medium temperature regions were due to the dual role played by the surface reaction between MOH and Pt-CO. Pt/C/Nafion(R) showed the highest resistance (10(6) Omega cm(-2)) compared with Pt-Ru/C (280 m Omega cm(-2)). The observed unfavorable electrochemical performance of the bimetallic Pt-Ru catalysts call be correlated with the observed variations in geometric structural information obtained from EXAFS and XANES measurements. The bimetallic catalysts investigated in this study must have formed as a Pt cluster covered with Ru and may not be in the expected alloy composition, which probably leads to the poor electrochemical performance.