We prepared the polyaniline (Pani) film and powder by chemical polymerization and doping with different dopants and also investigated the capability of Li//polyaniline cells after assembling. The oxidation/reduction potentials and electrochemical reaction of Li//polyaniline cells were tested by cyclic voltammetry technique. The Li//Pani-HCl cells with 10% and 20% conductors show a little larger specific discharge capacities than that without conductor. The highest discharge capacity of almost 50 mAh/g at 100th cycle is also achieved. However, Li//Pani-LiPF6 with 20% conductor shows a remarkable performance of ~90 mAh/g at 100th cycle. This is feasible value for using as the positive electrode material of lithium ion secondary batteries. It is also proved that the powder type electrode of Pani is better to use than the film type one to improve the specific discharge capacity and its stability with cycle.