This work aims to further the understanding of gold-based catalytic oxidation of n-octanol in liquid phase. Modification of catalysts with metal oxides additives (Fe or Mg) was used as a tool for transforming and stabilizing gold species. Structural, electronic and catalytic properties of gold catalysts were systematically investigated by means of DRS, H-2, CO FTIR, S-BET, EDS and SEM, HRTEM, SR-XRD, XANES, XPS and liquid phase n-octanol oxidation. Addition of modifiers affects Au electronic properties, but not the structural ones. Characterization results allow excluding Au3+ ions as candidates for active sites in n-octanol oxidation. In AufMg/TiO2, gold exhibited more reduced states while in Au/Fe/TiO2 gold was more oxidized; Au/TiO2 for intermediate oxidized states was found. The proper balance of oxidation states in the gold surface of Au/Mg/TiO2 can be responsible for its higher activity compared with AufFeiTiO(2) and Au/TiO2 towards n-octanol oxidation. Finally our approach shed light on the nature of active sites for n-octanol oxidation on gold and furthers the development of green base-free catalytic oxidation of alcohols. (C) 2016 Elsevier B.V. All rights reserved.