The Bi2Te3 and its derivative compounds are very interesting materials in the field of thermoelectric refrigeration at room temperature. An electrochemical deposition that is an alternative process of the standard synthesis is developed in our laboratory. The study of the reduction of TeIV+ and BiIII+ and their mixtures, in aqueous solvent, evidences the direct formation of near stoichiometric Bi2Te3 compounds. The electrodeposition is performed according to the reaction: 2BiO++3HTeO+2+13H++18e−→Bi2Te3↓+8H2OThe synthesis is realized in an acid electrolyte (HNO31M), allowing the stability of TeIV+ and BiIII+ salts. The Bi/Te ratio in the electroformatted films is varying with the solution composition and the applied current density. The X‐ray controls of all the compounds obtained by this method show only one product, with a good crystallinity. The patterns are consistent with the space group R‐3m of Bi2Te3. However, it should be noted orientation effects. The films exhibit qualitative thermoelectric prope...