The electrochemical behaviors of Bi(III), Te(IV), Sb(III) and their mixtures in DMSO solutions were investigated using cyclic voltammetry and linear sweep voltammetry measurements. On this basis, BixSb2-xTey film thermoelectric materials were prepared by potentiodynamic electrodeposition technique from mixed DMSO solution, and the compositions, structures, morphologies as well as the thermoelectric properties of the deposited films were also analyzed. The results show that BixSb2-xTey compound can be prepared in a very wide potential range by potentiodynamic electrodeposition technique in the mixed DMSO solutions. After anneal treatment, the deposited film prepared in the potential range of -200 to -400 mV shows the highest Seebeck coefficient (185 mu V/K), the lowest resistivity (3.34 x 10(-5) Omega m). the smoothest surface, the most compact structure and processes the stoichiometry (Bi0.49Sb1.53Te2.98) approaching to the Bi0.5Sb1.5Te3 ideal material most. This Bi0.49Sb1.53Te2.98 film is a kind of nanocrystalline material and (0 1 5) crystal plane is its preferred orientation. (C) 2010 Elsevier Ltd. All rights reserved.