Conventional electrochemical methods have been applied to study the oxidation of a possible alternative fuel for a direct oxidation fuel cell. The electrooxidation of dimethoxymethane (DMM) was investigated on the three low index planes, (100). (110) and (111) of platinum single crystals and compared with its oxidation on a platinum polycrystalline electrode. Among platinum electrodes, electroreactivity of DMM observed is Pt(111) > Pt(100) > Pt(110) similar to Pt poly. Hydrogen adsorption is limited by the presence of DMM, except for Pt(111) plane. In situ IR experiments show the presence of bands Of COads with all electrodes except Pt(111). This work shows that the mechanism of DMM electrooxidation is structure sensitive. A path takes place on Pt(100) and Pt(110) which is favourable to the formation of COads. Another path proceeds on Pt(111), where COads is not present and reaction does not occur at low potential. Results indicate that peak intensities are higher in perchloric acid than in sulphuric acid. So DMM adsorption is dependent on the specific adsorption of the anions. In situ IR reflectance spectroscopy identified some intermediates and reaction products of DMM adsorption and electrooxidation on Pt electrodes: COL (linearly bonded) and COB (bridge bonded), adsorbed CHO and CH3O species. methanol and CO2. The electrochemical and spectroelectrochemical experiments suggest a complex mechanism of DMM electrooxidation. (c) 2008 Elsevier Ltd. All rights reserved.