Deposition of Sb2Te3 thin films on polycrystalline Au substrates by electrochemical atomic layer epitaxy (ECALE) is described in this paper. Electrochemical aspects were characterized by means of cyclic voltammetry, anodic potentiodynamic scanning and coulometry. A steady ECALE deposition for Sb2Te3 compound could be attained after negatively adjusting the underpotential deposition (UPD) potentials of Sb and Te on Au in steps over the initial 40 cycles, and the potentials could be kept constant for the following deposition. A 400 cycle deposit, which was grown with the steady deposition potentials, was proved to be a single phase Sb2Te3 compound by X-ray diffraction analysis and SEM observation shows the deposit consisted of nanoscale particles with average size about 100 nm. The 2:3 stoichiometric ratio of the deposit was further verified by energy dispersive X-ray (EDX) quantitative analysis. (c) 2006 Elsevier Ltd. All rights reserved.