On X-ray photoelectron spectra of the Au-Rh/TiO2 catalysts the position of Au4f peak was practically unaffected by the presence of rhodium, the peak position of Rh3d, however, shifted to lower binding energy with the increase of gold content of the catalysts. Rh enrichment in the outer layers of the bimetallic crystallites was experienced. The bands due to Au-0-CO, Rh-0-CO and (Rh-0)(2)-CO were observed on the IR spectra of bimetallic samples, no signs for Rh+-(CO)(2) were detected on these catalysts. The results were interpreted by electron donation from titania through gold to rhodium and by the higher particle size of bimetallic crystallites.