TiO2 Degussa P25, TiO2 prepared by sol-gel submitted to sulfation pre-treatment and some metallized catalysts obtained by photodeposition of Au or Pt over the sulfated TiO2, were evaluated in the reaction of ethanol photo-oxidation. FT-IR spectroscopy was used to investigate the surface features of the photocatalysts, identifying adsorbed species and following the evolution of intermediate products in the ethanol photo-oxidation reaction. Nature of surface acidity in terms of Bronsted and Lewis centers was also studied. Results showed that sulfation pre-treatment and metallization were important factors influencing the selectivity. Acetaldehyde was the main oxidation product on sulfated TiO2; in the case of P25 also acetates production was observed. The photodeposition of metals had a detrimental effect on the selectivity to acetaldehyde; on metallized catalysts the formation of stable secondary intermediates was detected. Based on these findings, a reaction pathway for the ethanol photo-oxidation over the different photocatalysts, via acetaldehyde or via acetate formation is proposed. Crown Copyright (c) 2013 Published by Elsevier B.V. All rights reserved.