Layered polyaniline/polyanion composite films (PAn-X/PAn-PA) we re synthesized by electrochemical oxidation of aniline in aqueous acid solutions (HCl, HClO4) followed by polymerization in poly(styrene-4-sulfonic acid) (PSSH) solutions. The films consist of inner polyaniline (PAn layers doped with smaller size anions (X) and outer PSS-doped PAn layers. The resulting films showed high redox activities with cation-transfer properties in organic electrolyte solutions. The improved charge/discharge characteristics of the composite firms gave an expectation of higher energy density for the full cell with lithium negative electrode.