We demonstrate here a remarkable electrochemical activation of polypyrrole chains by doping with redox-active diphenylamine sulfonate anions. The organic redox dopant can not only serve as anionic counterions to enhance electrochemical activity of the polymer chains, but also contributes their redox capacity to the material. This organic-polymer composite exhibits a quite high reversible capacity of 115 mA h g-1, excellent rate capability and cycling stability, capable of serving as a low cost, and renewable cathode for Na-ion batteries. Since the chemical doping method is simple and easily extendable for a large variety of organic anions and polymer networks, it is possible to adopt this new strategy for creating low cost and electrochemically active polymer materials for widespread electric storage applications. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013