Conductive bilayer polymer films based on polymer electrolyte and polyaniline have been prepared by the electrochemical polymerization of aniline on an electrode covered with an ionic conductive polymer film. Electrochemical polymerization was carried out by the potentiodynamic method. The electrochemical properties of the bilayer films were investigated by cyclic voltammetry. The cyclic voltammograms indicated that the bilayer films have good redox stability, as well as reversibility, and show electrochemical activity in the solid state at room temperature. An all-solid-state rechargeable battery composed of lithium and this bilayer polymer film was tested. The preliminary experimental results showed that the battery can discharge in moderate electric current.