Five different bimetallic catalyst formulations (PtRu/C, PtSn/C, PtW/C, PtRh/C and PtOs/C) were prepared by reduction with sodium borohydride, and physico-chemically characterized by X-Ray Diffraction, Transmission Electron Microscopy, Temperature Programmed Reduction and X-Ray Photoelectron Spectroscopy. It was observed that in the case of the PtRu/C and PtRh/C a large fraction of the second metal enters the platinum lattice structure. The remaining metal, and in those catalysts in which no alloy was formed, its deposition was in a mixed metallic (Os) and/or oxide form, as TPR and XPS results displayed. Crystal sizes were in the range 3-5 nm, except for the case of the PtW/C in which there was a large agglomeration of platinum particles, as the TEM images confirmed. Electrochemical half-cell tests demonstrated the better performance of these bimetallic catalysts in terms of ethanol oxidation, with lower onset potential and larger current densities, particularly in the case of the PtOs/C, PtRu/C and PtRh/C materials, and to a lower extent in the case of the PtSn/C. Actual fuel cell tests at high temperature (150 and 200°C) confirmed the beneficial effects of increasing the temperature in terms of cell performance, with an increase in the performance, particularly in the cases of PtOs/C and PtRu/C. Finally, the product distribution was also assessed, observing a large conversion to CO2 by operating at high temperatures, particularly for PtRh/C at low current density, and for Pt/C at high current density (up to 35%), although acetaldehyde remained as the main oxidation product for all the catalysts. © 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.