Highly flexible, paper-like, free-standing polypyrrole and polypyrrole-LiFePO4 composite films were prepared using the electropolymerization method. The films are soft, lightweight, mechanically robust and highly electrically conductivity. The electrochemical performance of the free-standing pure PPy electrode was improved by incorporating the most promising cathode material, LiFePO4, into the PPy films. The cell with PPy-LiFePO4 composite film had a higher discharge capacity beyond 50 cycles (80 mA h/g) than that of the cell with pure PPy (60 mA h/g). The free-standing films can be used as electrode materials to satisfy the new market demand for flexible and bendable batteries that are suitable for the various types of design and power needs of soft portable electronic equipment.