Bilayered nanofilm electrodes made of polypyrrole (Ppy) and poly-2,5-dimercapto-1,3,4-thiadiazole (poly-DMcT) are produced by electrochemical means onto a carbon-fiber substrate, with the goal of preventing the loss of the electroactive mass of the disulfide and improving the electrode stability during the charge/discharge cycling process. Lightweight and high surface area composites are obtained by potentiostatically depositing a nanometric layer of Ppy onto a carbon fiber piece already supporting a layer of a potentiodynamically obtained poly(DMcT) film. The growth charge/mass ratio for the bilayered polymeric electrode is optimized, leading to a high electrochemical performance cathode with a stable specific capacity of ∼320mAhg−1 after 100 cycles.