The ethanol electro‐oxidation on platinum catalyst in acid media leads to the formation of acetaldehyde and acetic acid as main products. Another problem is the poisoning of the electro‐catalyst surface with CO formed during the fuel oxidation reaction. To increase the performance of Direct Ethanol Fuel Cells (DEFCs) it is necessary to develop new electrode materials or modification of the existing Pt catalysts. This work presents the electrochemical response to ethanol and CO oxidation of different compositional amorphous alloys obtained by ball milling technique, used as electrodes. Alloys with Ni59Nb40Pt0.6Rh0.4 and Ni59Nb40Pt0.6Rh0.2Ru0.2 composi‐tions were studied. The current density towards ethanol oxidation decreases with the presence of ruthenium; however, this electrode shows the best tolerance to CO, with lower surface coverage (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)