ABSTRACT The reduced graphene oxide/nonwoven fabric (rGO/NWF) composites have been fabricated through heating the NWF coated with the mixture of GO and HONH2·HCl at 130°C, during which the GO is chemically reduced to rGO. Then the composites of polypyrrole (PPy)/rGO/NWF have been prepared through chemically polymerizing pyrrole vapor by using the FeCl3·6H2O adsorbed on rGO/NWF substrate as oxidant. Finally, multiwalled carbon nanotubes (MWCNTs) are used as conductive enhancer to modify PPy/rGO/NWF through dip‐dry process to obtain MWCNTs/PPy/rGO/NWF. The prepared composites have been characterized and their capacitive properties have been evaluated in 1.0M KCl electrolyte by using two‐electrode symmetric capacitor test. The results reveal that MWCNTs/PPy/rGO/NWF possesses a maximum specific capacitance (Csc) of about 319 F g−1 while PPy/rGO/NWF has a Csc of about 277.8 F g−1 at the scan rate of 1 mV s−1 and that optimum MWCNTs/PPy/rGO/NWF retains 94.5% of initial Csc after 1000 cycles at scan rate of 80 mV s−1 which is higher than PPy/rGO/NWF (83.4%). Further analysis reveals that the addition of MWCNTs can increase the charger accumulation at the outer and inner of the composites, which is favorable to improve the stability and the rapid charge‐discharge capacity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41023.