Bismuth telluride-based compounds are among the most widely investigated semiconducting materials having excellent thermoelectric properties at the moderate temperature. Bi2Te3 can be coupled with Bi in adaptive series of layered (Bi2)m(Bi2Te3)n superlattices consisting of different stacking sequences of Bi double layers and Bi2Te3 blocks [1,2]. Commonly, these materials are synthesized via low temperature solid-state synthesis route [1]. In the given research, the layered superlattices were obtained by pulse electrodeposition from the acidic electrolyte containing Bi3+ and TeO2. Deposition has been carried out on the stainless steel substrate at room temperature without stirring. By tuning bath composition and electrodeposition conditions films having various Bi content ranged from Bi1.7Te3 to Bi7.3Te3 were obtained. The formation of these films was studied by cyclic voltammograms (CV) recorded during cathodic deposition and anodic oxidation. There are two well-defined peaks on the anodic branch of CVs: the first one corresponds to oxidation of interlayered bismuth, the second peak corresponds to Bi2Te3 anodic dissolution (Fig. 1a). Moreover, the detailed study by means of stripping voltammetry and EDX/XRD of partial anodic oxidation of (Bi2)m(Bi2Te3)n superlattices has revealed that the interlayered Bi removes and nearly stoichiometric Bi2Te3 films are formed (Fig. 1b).