Ethanol produced from cellulosic residues will be in large supply all over the world in the next decades. Undoubtedly, bioethanol will be used as a gasoline substitute or additive. Taking its future large availability into account, its use as feedstock for the chemical industry can also be foreseen. The ethyl acetate one-pot synthesis from ethanol is a good example of this new industry. This contribution aims to describe the dehydrogenative route of the ethyl acetate one-pot synthesis and also the role of the support using physical mixtures comprised of a dehydrogenation catalyst and four different oxides. The solids were characterized employing TPD of ethanol. CO2 and acetaldehyde and also pyridine adsorption. It was verified that acetaldehyde synthesized on the dehydrogenation catalyst migrates towards the oxide and reacts with the ethoxide species which are generated by the oxide basic sites. The resulting hemiacetal is dehydrogenated and the ethyl acetate obtained is desorbed. Oxides with strong basic sites generate the most active and selective systems for the ethyl acetate synthesis. (C) 2010 Elsevier B.V. All rights reserved.