Carbon-supported Pt-Sn catalysts commonly contain Pt-Sn alloy and/or Pt-Sn bimetallic systems (Sn oxides). Nevertheless, the origin of the promotion effect due to the presence of Sn in the Pt-Sn/C catalyst towards ethanol oxidation in acid media is still under debate and some contradictions. Herein, a series of Pt-x-Sn-y/C catalysts with different atomic ratios are synthesized by a deposition process using formic acid as the reducing agent. Catalysts structure and chemical compositions are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and their relationship with catalytic behavior towards ethanol electro-oxidation was established. Geometric structural changes are producing by highest Sn content (Pt-1-Sn-1/C) promoted the interaction of Pt and Sn forming a solid solution of Pt-Sn alloy phase, whereas, the intermediate and lowest Sn content (Pt-2-Sn-1/C and Pt-3-Sn-1/C, respectively) promoted the electronic structure modifications of Pt by Sn addition without the formation of a solid solution. The amount of Sn added affects the physical and chemical characteristics of the bimetallic catalysts as well as reducing the amount of Pt in the catalyst composition and maintaining the electrocatalytic activities at the anode. However, the influence of the Sn oxidation state in Pt-Sn/C catalysts surfaces and the alloy formation between Pt and Sn as well as with the atomic ratio on their catalytic activity towards ethanol oxidation appears minimal. Similar methodologies applied for synthesis of Pt-x-Sn-y/C catalysts with a small change show differences with the results obtained, thus highlighting the importance of the conditions of the preparation method. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.