This study compares the aerobic and anaerobic transformation of ethanol using FeVO4 and V2O5 catalysts. Despite their different structure, the two oxides showed very similar catalytic performances and their main product was acetaldehyde. However, in the absence of oxygen, the catalysts produced an equimolar amount of ethane and acetaldehyde, and this aspect has been little studied in the literature. In-situ XPS and DRIFT spectroscopy studies showed that the active species for the disproportionation of the alcohol into ethane and aldehyde was the reduced V3+ ion; nevertheless, the Fe in the FeVO4 catalysts was responsible for directing the reduction of metals toward the formation of a Fe-V-O spinel phase which was homogeneous and more stable than V2O5. Moreover, an in-situ DRIFT spectroscopy study showed that ethanol adsorbs in different ways on the surface of the catalysts during the reduction of samples (anaerobic reaction), forming H-bonded and dissociated ethoxy species, and giving rise to new surface OH groups that participate in the aldehyde/alkane formation. To conclude, a new mechanism of hydrogen transfer for the anaerobic ethanol disproportionation into ethane and acetaldehyde is proposed. This research completes the picture about ethanol oxidation to acetaldehyde on V-based catalysts, demonstrating that the catalytic behavior is mainly affected by the oxidation degree of the vanadium species which, in turn, depends on the reaction environment, and not on the structure itself.