A new all-polymer battery system has been developed. Polypyrrole and styryl-substituted dialkoxyterthiophene (poly(OC10DASTT) are used as the cathode and anode material, respectively. The anode electrode is prepared by directly casting undoped neutral poly(OC10DASTT) from chloroform solution on two different substrates (current-collectors), carbon-fibre mat or Ni/Cu-coated nonwoven polyester. Poly(OC10DASTT) exhibits electroactivity on these two substrates, and batteries containing the polymers show different charge/discharge properties. All the batteries show a high discharge efficiency of over 94%, and a discharge capacity of 39.1mAhg−1 is obtained for the battery with an anode that consists of poly(OC10DASTT) on Ni/Cu-coated nonwoven polyester.