Nanoporous carbon/MnO2 (C–MnO2) composites with foam-like structure based on modified nitrile butadiene rubber were achieved by thermal treatment, followed by alkaline solution etching and dipping method. The XRD, nitrogen adsorption and desorption, and SEM and TEM were used to characterize the microstructure of the obtained C–SiO2, C and C–MnO2. Finally, all the obtained samples have been used in three-electrode system to study the electrochemical properties including cyclic voltammetry, galvanostatic charge/discharge and AC impedance for supercapacitor. The study found that the specific capacity of C–MnO2 electrode material for supercapacitor could reach as high as 109 F/g under the current density of 0.5 A/g, which is much higher than those of the other two. These superior electrochemical properties are attributed to the synergistic effect MnO2 particles with the C matrix which functions as a conductive support.