Herein we report a direct synthesis of FeSe nanostructure with tetragonal phase by electrochemical deposition. The FeSe thin films have been successfully deposited onto indium doped tin oxide coated conducting glass (ITO) in the aqueous electrolytic bath containing FeSO(4) and SeO(2). The deposition mechanism was inferred that the Se(4+) ions are reduced to Se and successively oxidized to Se(2-), which was immediately involved with Fe(2+) to form the tetragonal structure. This new approach promises to be of strong significance for succeeding fabrication of iron-based superconductor. (C) 2011 Elsevier B.V. All rights reserved.