The addition of small quantities of gold to the surface of supported nickel catalysts has been described as a means to retard carbon formation during hydrocarbon steam reforming. Calculations by others have indicated that gold locates at the most catalytically active (step and edge) sites that also serve as nucleation sites for carbon formation. In this paper, we describe experiments to characterize the Ni-Au interactions on bimetallic Au-Ni/MgAl2O4 catalysts at various Ni and Au loadings. The catalyst structure was investigated using EXAFS/XANES spectroscopy and adsorption-desorption measurements with H-2 and N2O. Evidence for surface alloy formation is provided in the Ni K-edge and Au L-III-edge EXAFS measurements of Au-promoted 8.8% Ni/MgAl2O4, especially at An loadings <= 0.2 wt%. At higher Au concentrations, there is evidence of a combination of alloy and segregated Au species. H-2 chemisorption and N2O temperature-programmed desorption (TPD) measurements showed a significant decrease in total surface sites, or surface site reactivity, on Au-modified Ni/MgAl2O4 catalyst. The XANES structure is consistent with perturbation of the electronic structure of both the Ni and Au atoms as a result of alloy formation. TGA studies with steam/n-butane feed confirmed the ability of An to retard coke deposition under low S/C reforming conditions, although carbon formation was not fully suppressed. When testing for methane steam reforming, a lower initial activity and deactivation rate resulted from Au promotion of the Ni catalyst. However, both catalysts showed a declining activity with time. The lack of a direct correlation between the surface characterization results and catalytic activity is most likely a result of decreasing effectiveness of the surface alloy with increasing temperature. (c) 2006 Elsevier Inc. All rights reserved.