This work reports studies of ethanol oxidation on Pt-Sn/C catalysts with nearly the same particle size and identical overall composition having different amounts of oxide and alloyed phases. Results of characterization of physical properties by transmission electron microscopy (TEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), X-ray photoelectron spectroscopy (XPS), and in situ dispersive X-ray absorption spectroscopy (DXAS) are presented. The variation in the amount of oxide and alloyed phases, promoted by heat treatments in mild temperature conditions, does not produce any significant particle growth. Cyclic voltammetry and oxidation of adsorbed CO in acid medium are used to probe the surface conditions. Data on the electrocatalytic activity towards ethanol oxidation, obtained by potential sweeps and chronoamperometry, are discussed and correlate well with the physical properties. This study, carried out in the absence of composition and particle size effects, shows that the electrocatalytic activity towards ethanol oxidation is strongly influenced by the changes in the amounts of Sri in alloyed and oxidized forms, and that the increase in the amount of alloy at expense of the oxides improves the catalytic activity. (C) 2009 Elsevier B.V. All rights reserved.