To obtain polypyrrole (PPy) films with high area specific capacitance as electrode material for supercapacitors, the multi-step polymerization method was proposed for preparing PPy thick films with polymerization charge of 8, 10, and 12 mAh·cm-2, doped with Cl- and p-toluenesulfonate (TOS-), respectively. The capacitance properties of the PPy films were investigated by galvanostatic charge/discharge, cyclic voltammetry (CV), and electrochemical impedance spectrum (EIS) technologies. The section morphology of the PPy films was observed by using field emission electron scanning microscope (SEM). The results showed that two kinds of even porous PPy films with area specific capacitance up to 5 F·cm-2 could be obtained by multi-step method. Moreover, the mass specific capacitance (referring to the masses of polymer and doping ions) of PPy-Cl could reach 330 F·g-1, and the value of PPy-TOS could reach 191 F·g-1, which were similar with that of PPy thin films. However, the discharge rate of the PPy-TOS film was more rapid than that of the PPy-Cl film. In addition, the growth processes of PPy films from one-step
polymerization method and multi-step polymerization method were discussed.