Both the dehydrogenative and the oxidative routes for the one-pot ethyl acetate synthesis from ethanol were studied using physical mixtures of Cu/ZnO/Al2O3 or PdO/m-ZrO2 with three different ZrO2. The characterization of these catalysts and oxides was carried out by N-2 physisorption, pyridine adsorption, CO2 thermo desorption, dynamic light scattering and X-ray diffraction. It was inferred that the second step of the dehydrogenative and oxidative routes, i.e. acetaldehyde and ethanol or ethoxide condensation are very similar. Moreover, it could be verified that this condensation occurs on the ZrO2 surface and also that the basic properties of these oxides influence the catalytic behavior of the physical mixtures (Cu/ZnO/Al2O3 + ZrO2 and PdO/m-ZrO2 + ZrO2). The transport of acetaldehyde from the dehydrogenative sites to the ZrO2 surface might be associated with the spillover phenomenon. (C) 2010 Elsevier B.V. All rights reserved.