In the present work, the role of the structural characteristics of Pt-based catalysts on the single direct ethanol proton exchange membrane fuel cell (PEMFC) performance is examined. Several PtM/C (M = Sn, Ru, Pd, W) catalysts were characterized by means of transmission electron microscopy (TEM) and X-ray diffraction (XRD) and then evaluated as anode catalysts in single direct ethanol fuel cells. XRD spectra showed that Pt lattice parameter decreases with the addition of Ru or Pd and increases with the addition of Sn or W. According to the obtained experimental results, PtSn catalysts presented better electrocatallytic activity towards ethanol electro-oxidation. Based on these results, PtSn/C catalysts with different Pt/Sn atomic ratio were tested and compared. The maximum power density values obtained were correlated with the structural characteristics of the catalysts. A volcano type behaviour between the fuel cell maximum power density and the corresponding atomic percentage of Sn (Sn%) was observed. It was also observed that Sn% affects almost linearly the PtxSny, catalysts' lattice parameter. (C) 2007 Elsevier B.V. All rights reserved.