Carbon-supported Pt and Pt3Co catalysts with a mean crystallite size of 2.5 nm were prepared by a colloidal procedure followed by a carbothermal reduction. The catalysts with same particle size were investigated for the oxygen reduction in a direct methanol fuel cell (DMFC) to ascertain the effect of composition. The electrochemical investigations were carried out in a temperature range from 40 to 80 degrees C and the methanol concentration feed was varied in the range 1-10 mol dm(-3) to evaluate the cathode performance in the presence of different conditions of methanol crossover. Despite the good performance of the Pt3Co catalyst for the oxygen reduction, it appeared less performing than the Pt catalyst of the same particle size for the cathodic process in the presence of significant methanol crossover. Cyclic voltammetry analysis indicated that the Pt3Co catalyst has a lower overpotential for methanol oxidation than the Pt catalyst, and thus a lower methanol tolerance. Electrochemical impedance spectroscopy (EIS) analysis showed that the charge transfer resistance for the oxygen reduction reaction dominated the overall DMFC response in the presence of high methanol concentrations fed to the anode. This effect was more significant for the Pt3Co/KB catalyst, confirming the lower methanol tolerance of this catalyst compared to Pt/KB. Such properties were interpreted as the result of the enhanced metallic character of Pt in the Pt3Co catalyst due to an intra-alloy electron transfer from Co to Pt, and to the adsorption of oxygen species on the more electropositive element (Co) that promotes methanol oxidation according to the bifunctional theory. (C) 2009 Elsevier Ltd. All rights reserved.