The galvanic cell method has been used for the synthesis of BaMoO4 double oxide film in barium hydroxide aqueous solutions. This method could resolve the repulsion of the electric field on the anode and favor the mass transfer of cations. The crystal growth in the solution is easier compared with the traditional electrochemical deposition with applied power. The deposition process of the galvanic cell technique has been investigated by deposition time, pH, and ion concentration, and the basic features of this method are discussed.