Polytriphenylamine (PTPAn) was chemically synthesized and tested as a cathode material for high-rate storage and delivery of electrochemical energy. It is found that the polymer has not only superior high power capability but also high energy density at prolonged cycling. At a moderate rate of 0.5C, PTPAn gives a high average discharge voltage of 3.8V and quite a high capacity of 103mAhg−1, which is very close to the theoretical capacity (109mAhg−1) as expected from one electron transfer per triphenylamine monomer. Even cycled at a very high rate of 20C, the polymer can still deliver a capacity of 90mAhg−1 at 1000th cycle with a nearly 100% coulombic efficiency. The excellent electrochemical performances of PTPAn are explained from the structural specificity of the polymer where the radical redox centers are stabilized and protected by conductive polymeric backbone, making the radical redox and charge-transporting processes kinetically facile for high-rate charge and discharge.