This work describes the methanol, ethanol and formic acid oxidation using a metallic bilayer electrodeposited on a platinum substrate. Firstly, one monolayer of ruthenium was deposited on the substrate and over it a 1.1 layer of metallic platinum. In the blank solution it was observed that the electrochemical behavior of both the Pt/Ru/Pt and bulk Pt were very similar, except in the oxygen evolution potential region. Using X-ray photoelectronic spectroscopy (XPS) it was not possible to identify the presence of Ru atoms on the bilayer surface. The electroactive area and the RMS roughness factor measured with atomic force microscopy (AFM) for both materials are the same. A CO monolayer oxidation procedure confirmed that the systems have the same real surface area and also showed a shift in the negative direction for 54 mV on the CO peak potential for the bilayer. For the voltammetric organic molecules oxidation, an enhancement in the current densities of 350, 390 and 420% was observed for ethanol, methanol and formic acid, respectively, for the bilayer system compared to the bulk Pt electrodes. Also, a decrease of I 10 mV in the beginning of the ethanol oxidation process was observed over the bilayer system compared to bulk Pt. (c) 2006 Elsevier B.V. All rights reserved.