Highly flexible and bendable free-standing polypyrrole-para (toluene sulfonic acid) (PPy-pTS) films were prepared using the electropolymerization method. The films are soft, lightweight, mechanically robust, and highly electrically conductive. The films display a cauliflower-like structure consisting of micron-scale spherical grains, which are related to dopant intercalation in the polymeric chains. The electrochemical behaviour of the free-standing films was examined as cathode against lithium counter electrode. Electrochemical tests demonstrated that the PPy-pTS film with 30min deposition time exhibited higher discharge capacity (85mAhg−1) beyond 80 cycles than the PPy-pTS films with 1h deposition time (76mAhg−1) and 2h deposition time (55mAhg−1) at 0.1mAcm−2 over a potential range of 2.5–4.3V. The free-standing films can be used as electrode materials to satisfy the new market demand for flexible and bendable polymer batteries.