We propose a simple and novel route for the surface microstructuring of tough materials (glassy carbon, SiC, W and Mo) through a solid electrochemical reaction at a microcontact between the oxide ion conductor and target substrate. More specifically, the surface of materials was locally oxidized by an anodic electrochemical reaction with the oxide ion conductor via the microcontact under a dc bias. Since the oxidation products of the targets were gaseous or sublimable, a fine-patterned surface was obtained as a result of the continuous consumption of the oxidation products formed at the microcontact. The success of the proposed method may stimulate such conventional applications of oxide ion conductors. (C) 2009 Elsevier B.V. All rights reserved.