The carbon nanotubes (CNTs) have been loaded on the melamine foam (MF) to form the composite (CNTs/MF) by dip-dry process, then polypyrrole (PPy) is coated on CNTs/MF (PPy/CNTs/MF) through chemical oxidation polymerization by using FeCl3·6H2O adsorbed on CNTs/MF as oxidant to polymerize the pyrrole vapor. Finally, CNTs are coated on the surface of PPy/CNTs/MF to increase the conductivity of the composite (CNTs/PPy/CNTs/MF) by dip-dry process again. The composites have been characterized by X-ray diffraction spectroscopy, scanning electron microscopy and electrochemical method. The results show that the structure of the composites has obvious influence on their capacitive properties. According to the galvanostatic charge/discharge test, the specific capacitance of CNTs/PPy/CNTs/MF is about 184 F g−1 based on the total mass of the composite and 262 F g−1 based on the mass of PPy (70.2 wt % in the composite) at the current density of 0.4 A g−1, which is higher than that of PPy/CNTs/MF (120 F g−1 based on the total mass of the composite and 167 F g−1 based on the mass of the PPy). Furthermore, the capacitor assembled by CNTs/PPy/CNTs/MF shows excellent cyclic stability. The capacitance of the cell assembled by CNTs/PPy/CNTs/MF retains 96.3% over 450 scan cycles at scan rate of 20 mV s−1, which is larger than that assembled by CNTs/PPy/MF (72.5%). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39779.