The composites of polypyrrole (PPY) and MnO2 have been prepared through chemical oxidation of pyrrole monomer and MnO2 suspension with ammonium peroxysulfate at low temperature. The morphology and structure of materials were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), Transmission electron microscopy (TEM), thermal gravity analysis ‐ differential thermal gravity (TG‐DTG), and X‐ray diffraction (XRD) measurements. The electrochemical properties of the composite were investigated by galvanostatic charge–discharge and electrochemical impedance spectroscopy. The specific capacitance of the composite electrode is 352.8 F/g at a current of 8 mA/cm2 in Na2SO4 electrolyte of 0.5 mol/L, which is much higher than that of 246.2 F/g and 103.5 F/g of PPY and MnO2, respectively. A convenient and effective technique has been developed to fabricate composite materials of PPY and MnO2 promising for designing new capacitors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013