Stainless-steel mesh electrodes coated with polybithiophene, obtained by electrochemical polymerization (constant potential and constant current), have been investigated as cathode materials in a lithium–polybithiophene rechargeable battery by cyclic voltammetry, electrochemical impedance spectroscopy and long-term charge–discharge cycling process. The effects of different growth methods on the surface morphology of the films and the charge–discharge capacity are discussed in detail. The results show that polybithiophene-hexafluorophosphate is a very promising cathode material for manufacturing lithium–polymer rechargeable batteries with a highly stable discharge capacity of 81.67mAhg−1 after 50 cycles.