Hierarchical porous polypyrrole films have been successfully prepared by interfacial self-assembly polymerization with assistance of the long-chain surfactant OP10. The molecular structure

micromorphology and electrochemical performance of obtained polypyrrole were characterized. The results showed that introducing OP10 into interfacial polymerization had no effect on the molecular structure of obtained polypyrrole but a significant impact on its micromorphology. When the dosage of OP10 was optimized at 0.02 g

polypyrrole could self-assemble to form a hierarchical porous structure including nanopores (~100 nm)

submicron pores (200-1000 nm) and micron pores (1-3.5 μm). Because of relatively larger active surface area and higher total pore volume

hierarchical porous polypyrrole

as the electrode material

possessed a maximum specific capacitance up to 357 F·g-1 which is 70% higher than that prepared by traditional interfacial synthesis at the same conditions. Furthermore

87.6% of the initial specific capacitance was still retained even after 2000 charge-discharge cycles

indicating the excellent cycling stability of the prepared polypyrrole.