Abstract: Polypyrrole (PPy) thin films were synthesized via interfacial chemical oxidation method using FeCl₃ as oxidant and pyrrole as monomer with the addition of phase transfer catalysts (PTC), 18C6 crown ether (CE) and polyethylene glycol 1000 (PEG). Scanning Electron Microscope (SEM), Thermo-Gravimetric (TG) analysis, and electrochemical analysis (Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS)) were used to characterize the structure and property of PPy. Results show that addition of PTC strongly accelerates the diffusion of oxidant to oil phase, inhabits the diffusion of monomer to water phase, indicating that polymerization of PPy is a diffusion-controlled process. PPy films show ordered structure. With the addition of 0.04 mol/L CE, the specfic capacitance of PPy films is 237.95 F/g, which is 4 times higher than PPy films(47.01 F/g) synthesized without CE, and the material is cyclic stably.