The performance of a composite film of polypyrrole (PPy) and poly(4-styrenesulfonate) (PSS) was studied in combination with an organic electrolyte as a possible lithium battery cathode. The composite film had a fairly flat morphology and exhibited electroactivity in organic electrolyte solutions using dimethylsulfoxide and propylene carbonate (PC) solvents. We confirmed that during the redox process the film charge was compensated with cations. A lithium cell consisting of the composite film as a cathode and a LiClO4-PC electrolyte worked as a rechargeable battery. The energy density of the PPy/PSS cathode was calculated to be 220 Wh liter-1 and the average output voltage of the rechargeable cell was 2.9 V.