The use of ethanol and bioethanol demonstrates the viability of alternative fuels to gasoline with optimum energy purposes. The development of suitable catalysts is fundamental to improve the electrical performance in Direct Alcohol Fuel Cells (DAFCs). For that reason, a series of amorphous Ni(59)Nb(40)Pt(0.6)Y(0.2)Z(0.2) (PtYZ) alloys adding three different transition metals (Y, Z = Cu, Ru and Sn) were manufactured by Mechanical Alloying (MA) method. The low amount of Pt and bifunctional-electronic role of cocatalysts was analyzed using electrochemical techniques such as Cyclic Voltammetry (CV), chronoamperometry and CO stripping experiments. Concerning to reactivity towards alcohol electrooxidations, alloys with Cu showed the best catalytic performance. However, its use is limited by Cu dissolution in acid media. The PtYZ catalysts showed higher CO tolerance, achieving smaller rates of poisoning (delta) for PtRuSn alloy. CO stripping reveals that CO oxidation on alloys with Ru takes place at lower electrode potentials. The experimental results showed better electric performance, but higher poisoning of the catalytic surface for bioethanol electrooxidation. Acetaldehyde and formic acid were found in bioethanol by HPLC, influencing the electrochemical response. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.