In the present investigation ethanol-water mixtures were directly fed to a yttria stabilized zirconia (YSZ) electrochemical reactor operated in a fuel cell mode and the preliminary results are presented and discussed. Polycrystalline films of platinum (Pt) and silver (Ag) were, respectively, tested as anode catalysts in a wide range of experimental conditions while the cathode was exposed to the atmospheric air. The single direct ethanol solid oxide fuel cell (DE-SOFC) tests were performed in order to investigate separately Pt and Ag’s activities towards ethanol steam reaction and fuel cell performance ( and ). In both cases the products were on-line analyzed by a mass spectrograph, a gas chromatograph and a series of gas analysers under fuel cell mode of operation. The results showed that even at high temperature values the main products were , , , , and . Furthermore, as expected the single DESOFC performance was improved as the temperature increased. However, a relatively poor fuel cell performance has been obtained in both cases, which could be attributed to the following reasons: the relatively low (for YSZ electrolyte) operation temperature, the presence of homogeneous reactions, and the cell configuration.