Alcohols oxidative coupling to esters has a great importance because of their use in different fields. For this purpose, we report a study on oxidative cross-coupling of methanol with ethanol, in the gas phase, on vanadium dopped copper ferrites. The samples have been synthesized by sol-gel combustion, substituting the Fe3+ cations with V5+. The surface properties and the catalysts composition play an important role for the products distribution. The presence of the spinel structure, alongside magnetite and teronite phases, as well as the existence of the redox couples Cu2+/Cu+ and Fe3+/Fe2+ influences both the catalytic activity and the products yield. The change in the oxidation state of copper, from Cu2+ to Cu+, and respectively iron, from Fe3+ to Fe2+, determine occurrence of the oxygen vacancies into the crystal lattice that could represent the main active sites. In the same time, the presence of O2- with moderately basicity plays an important role in aldehyde and esters formation. [GRAPHICS] .