We investigated the influence of metal loading in gold catalysts supported on titania, either unmodified or Lamodified, on their catalytic performance and the formation of active sites for selective oxidation of n-octanol under mild conditions. Catalysts were characterized by BET, EDX, ICP, HRTEM, FTIR CO and XPS. Gold content had a significant effect on the catalytic properties of unmodified catalysts: activity of Au/TiO2 increased by increasing the metal load. However, in the case of a lanthanum-modified support samples, an increase of gold content from 0.5 to 4 wt.% had no effect on its activity (ca. 40% conversion after 6 h for all catalysts). This catalytic behavior is due to a change in the surface concentration of Au+ ions. For the unmodified catalysts, the surface concentration of Au+ ions increased with increasing gold loading, and, as a consequence, a significant increase in activity was observed. For La-modified catalysts, the surface concentration of Au+ ions is almost the same for all gold concentrations; as a result, no increase in activity was observed with the increase in gold content. It points to Au+ ions as the most probable active sites for the studied reaction.