Polyaniline (PANI)-poly (p-styrenesulfonic acid) (PSS) composite was prepared by thermal post-polymerization of PANI-p-styrenesulfonic acid (SSA) composite. A PANI-SSA composite was prepared by mixing PANI/N-methyl-2-pyrrolidinone solution with SSA aqueous solution. The PANI-SSA composite film was prepared by casting the composite onto an ITO glass plate. The cast film was converted to PANI-PSS film by heating at 100 degrees C for 3 h (post-polymerization process). The PANI-PSS modified ITO electrode showed electrochemical responses based on the redox reaction of PANI-PSS composite in the organic electrolyte solution, for example, propylene carbonate containing 1 mol dm(-3) LiClO4. The PANI-PSS composite was a cation -doping polymer composite. The composite was also modified on a porous carbon material (Reticulated Vitreous Carbon(TM), RVC, Energy Research and Generation, Inc.). The PANI-PSS modified RVC electrode showed similar electrochemical behaviour as the PANI-PSS modified ITO electrode. Model secondary lithium cells, Li/1 mol dm(-3) LiClO4-propylene carbonate/PANI-PSS modified RVC electrode, were constructed and charge-discharge cycling tests were carried out. The cell showed about 60% coulombic efficiency under high current density cycling conditions (3.8 A g(-1), per gram of PANI-PSS modified RVC electrode).