The three-dimensional microporous polypyrrole/polysulfone (PPY/PSF) composite film was fabricated via a simple polymerization method. The morphology structure and chemical composition of the composite film were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), respectively. The electrochemical properties of the composite film electrode were evaluated by cyclic voltammetry, galvanostatic charging-discharging and electrochemical impedance spectroscopy. The material exhibits excellent capacitance performance including high capacitance of 500 F g(-1) at 0.3 A g(-1) current density, good cycle stability in 800 continuous cycles (only 4.5% decay after 800 cycles at 0.3 A g(-1)), and low inter resistance. The good property of the PPY/PSF electrode should be attributed to its structural features, including two-layer microporous structure which facilitates the penetration of electrolytes into the inner surface, high surface area which provides more active sites. These results show that the composite film is a promising candidate for high energy electrochemical capacitors. (C) 2015 Elsevier B.V. All rights reserved.