The ethanol and bioethanol electro-oxidation on amorphous Ni59Nb40Pt0.6Ru0.4, Ni59Nb40Pt0.6Sn0.4 and Ni59Nb40Pt0.6Ru0.2Sn0.2 electro-catalysts was analyzed by electrochemical techniques such as Cyclic Voltammetry (CV) and chrono-amperometry. The different micro-particulated amorphous alloys were obtained by Mechanical Alloying (MA) during 40 h, being characterized by Differential Scanning Calorimetry (DSC) and X-Ray Diffraction (XRD) to verify their amorphous nature. The minimum amount of platinum and the addition of co-catalysts were found to have a significant effect on catalytic response of anodic reaction. Although the tri-catalytic alloy provides smaller rate of poisoning (delta) than bi-catalytic alloys, the presence of tin does not improve the ethanol/bioethanol electro-oxidation reaction due to limit the distribution of platinum atoms by the ligand effect, avoiding alcohol adsorption. Concerning the reactivity towards bioethanol electro-oxidation, the current densities are considerably higher than ethanol one for all amorphous catalysts. The presence of small amount of acetaldehyde and formic acid in bioethanol, provides a synergic effect during electrooxidative process. On the other hand, the voltammograms for CO stripping clearly show that alloy with ruthenium possesses a better CO tolerance, decreasing the onset potential 20 and 16 mV with regard to Ni59Nb40Pt0.6Sn0.4 and Ni59Nb40Pt0.6Ru0.2Sn0.2 alloys respectively. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.