AbstractTo investigate the interaction of rhenium with several supports, a preliminary study on pure rhenium compounds has been carried out in order to achieve a better understanding of their surface chemical properties.To this end X‐ray photoelectron spectroscopy (XPS) and thermogravimetry (TG) methods have been applied.The results show that metallic rhenium, ReO2and ReO3are covered with Re(VII). By heating in H2, NH4ReO4and rhenium oxides are reduced to metallic rhenium in different temperature ranges. In the case of Re2O7a spillover effect has been found when platinum is present. For ReO3and ReO2a morphological model has been described on the basis of combined XPS, TG and surface area measurements.The binding energy values of the different rhenium oxidation states have been assessed and their variation with the oxidation number briefly discusse