Mono- and bimetallic platinum-rhenium reforming catalysts with the content of each metal of 0.3 wt.% were studied by H-2 and O-2 adsorption, TPR and X-ray absorption techniques. It has been demonstrated that combination of hydrogen and oxygen adsorption at ambient temperature is a sensitive tool to monitor Pt-Re interaction in reforming catalyst. The technique was applied to the investigation of the effect of various pretreatments on the state of Pt and Re in bimetallic catalysts. It was shown that the degree of surface hydroxylation essentially affects aggregation or segregation of Pt and Re during reduction step. Thus, pretreatments at severe conditions, leading to dehydroxylation of the alumina surface, resulted in Pt-Re segregation evidenced by an increase of H-2 adsorption due to higher amount of exposed Pt atoms and a decrease Of O-2 adsorption due to a smaller fraction of Re atoms in close contact to Pt. On the contrary, treatments at moderate conditions, preserving surface hydroxyl groups, favored the transport of ReOx species to Pt during the reduction step and resulted in the aggregation of metals followed by a decrease of H-2 adsorption and an increase Of O-2 adsorption. These conclusions were confirmed by TPR and X-ray adsorption experiments. (c) 2007 Elsevier B.V. All rights reserved.