Gold catalysts supported on ceria doped by Sm and Al were studied. The influence of the preparation method, as well as the nature of dopants on the structure, properties and WGS activity are investigated. The applied methods of preparation cause the modification of ceria in a different extent. In the sample prepared by co-precipitation (CP) and doped by Al, the vacancies are located within the bulk of ceria structure, whereas in the corresponding AuCeSmCP sample the vacancies are located most likely around Sm and the ceria structure seems to be better ordered than the Al doped ceria. There is no distinct correlation between the reducibility and WGS activity of the studied catalysts. The Au 4f XPS spectra of fresh samples reveal higher contribution of dispersed form of Au for Sm doped catalysts than for the corresponding Al doped samples. The Ce 3d XPS spectra disclose also a higher concentration of Ce3+ evaluated before the catalytic operation for Sm doped catalysts as compared with the Al doped fresh samples. The observations by "in situ" FT-IR spectroscopy agree well with the model of active sites and the, mechanism of the WGS reaction proposed recently by some of us. The amount of formate species observed on the AuCeSmCP is higher than that on the AuCeAlCP catalyst and parallels the catalytic activity. The higher concentration of active sites on the surface of the AuCeSmCP catalyst facilitates the dissociation of water. (C) 2010 Elsevier B.V. All rights reserved.