The unique catalytic activity of supported Au nanoparticles has been ascribed to various effects including thickness/ shape, the metal oxidation state, and support effects. Previously, we reported the synthesis of ordered Au monolayers and bilayers on TiOx, with the latter being significantly more active for CO oxidation than the former. In the present study, the electronic and chemical properties of ordered monolayer and bilayer Au films have been characterized by infrared reflection adsorption spectroscopy using CO as a probe and ultraviolet photoemission spectroscopy. The Au overlayers are found to be electron-rich and to have significantly different electronic properties compared with bulk Au. The common structural features of ordered Au bilayers and Au bilayer nanoparticles on TiO2(110) are described, and the exceptionally high catalytic activity of the Au bilayer structure related to its unique electronic properties.