The actual state of the art in the reduction of perrhenate ions on noble metals is reviewed and discussed. Also, with the aim of contributing to better knowledge of this process, results of several experiments are presented. For the first time, spectroscopic evidence on the nature of the deposited rhenium layer on Pt and Rh and the detection of an intermediate in the reduction pathway toward metallic rhenium is provided. The role of the substrate in the electroreduction of perrhenate ions in aqueous acid media is emphasized, because it is directly associated with the formation of different H-containing species as reducing agents. Thus, those metals capable of adsorbing H atoms are able to reduce ReO4- to ReO2 by H-ad at potentials more positive than that of the hydrogen evolution reaction. Moreover, H-ad reacts with the ReO2 layer previously deposited, resulting in the formation of Re(III)-soluble species, which subsequently undergo disproportionation to Re and ReO2. For metals that are not capable of adsorbing H, i.e., Au, molecular hydrogen is the reducing agent, leading to the formation of metallic Re. In addition, ReO4- is chemically reduced to metallic Re by hydride. (C) 2003 Elsevier Science (USA). All rights reserved.