Gold catalysts supported on iron oxide have been characterized by X-ray photoelectron spectroscopy (XPS). Depending on the method of preparation and pretreatment, different gold species have been detected on the catalyst surface. In the absence of thermal treatment, the XPS spectra of the impregnated samples show the formation of gold(III) (oxy)chloride species. No metallic gold is formed. Both metallic and oxidized gold species are instead present on the surface of the samples prepared by coprecipitation. Oxidized gold(III) species are predominant on the uncalcinated catalysts. After treatment at high temperature and/or under reaction conditions the amount of metallic gold increases. The XPS data have been correlated with the activity of the investigated catalysts in the oxidation of carbon monoxide at low temperature.