Bismuth selenide thin films were grown on Pt substrate via the route of electrochemical atomic layer epitaxy (ECALE) in this work for the first time. The electrochemical behaviors of Bi and Se on bare Pt, Se on Bi-covered Pt, and Bi on Se-covered Pt were studied by cyclic voltammetry and coulometry. A steady deposition of Bi2Se3 could be attained after negatively stepped adjusting of underpotential deposition (UPD) potentials of Bi and Se on Pt in the first 40 deposition cycles. X-ray diffraction (XRD) analysis indicated that the films were single phase Bi2Se3 compound with orthorhombic structure, and the 2:3 stoichiometric ratio of Bi to Se was verified by EDX quantitative analysis. The optical band gap of the as-deposited Bi2Se3 film was determined as 0.35 eV by Fourier transform infrared spectroscopy (FTIR), which is consistent with that of bulk Bi2Se3 compound. (C) 2009 Elsevier Ltd. All rights reserved.