The properties of Bi surfaces with different roughnesses were characterized by electron microscopy, cyclic voltammetry, and impedance spectroscopy. Two different strategies were used for preparation of porous bismuth layers onto Bi microelectrode surface in aqueous 0.1 M LiClO4 solution. Firstly, treatment at potential E < -2 V (vs. Ag|AgCl in sat. KCl) has been applied, resulting in bismuth hydride formation and decomposition into Bi nanoparticles which deposit at the electrode surface. Secondly, porous Bi layer was prepared by anodic dissolution (E = 1 V) of bismuth electrode followed by fast electroreduction of formed Bi3+ ions at cathodic potentials E = -2 V. The nanostructured porous bismuth electrode, with surface roughness factor up to 220, has negligible frequency dispersion of capacitance and higher hydrogen evolution overvoltage than observed for smooth Bi electrodes. (C) 2010 Elsevier Ltd. All rights reserved.