The adsorption and dissociation of water has been examined between 80 and 500 K on two different Re surfaces — Re(0001) and a stepped vicinal Re[16(0001) × 2(1 1 ̄ 01)] — using TDS, LEED, AES and ESDIAD (Electron Stimulated Desorption Ion Angular Distribution). Above 250 K, the adsorption is dissociative on both surfaces but the extent of dissociation is larger on a stepped than on a basal face. During adsorption, evolution of hydrogen is observed after an induction period. This phenomenon is related to the formation of OH radicals. The adsorption on Re(0001) is molecular at 80 K. Several steps could be observed: adsorption of isolated molecules, formation of bilayer clusters ordered in two ( 3 × 3 )R30° structures and finally the formation of a multilayer. Situations of non-uniform coverage of the surface have been found in which multilayer patches, bilayer clusters and uncovered areas are simultaneously present. Three molecular water desorption peaks can be observed. Peaks A (180 K) and B (150 K) are produced by desorption from the first bilayer and peak C (140–150 K) is related to the desorption from the multilayer. Furthermore, molecules in the first bilayer are partly dissociated as shown by desorption of hydrogen between 250 and 450 K. ESDIAD and LEED experiments have shown that desorption, manifested by peak A, occurs after a reconstruction of the bilayer, ordered in two (2 × 2) structures, resulting from a displacement of water molecules from the on-top sites to three fold sites. The latter molecules dissociate between 190 and 240 K giving OH ads + H ads. Dissociation of OH would occur only above 360 K. On stepped Re dissociative adsorption occurs on steps, even at 80 K, while adsorption remains molecular on terraces. This might be accounted for by the lowering of the activation barrier of the dissociation on steps.