For improving the conductivity of porous carbon and the utilizations of its pore structures, a hierarchical porous carbon (HPC) had been developed with highly fluffy three-dimensional (3D) continuous network structure. Using the HPC as a support, a novel MnO2@HPC composite with 3D interpenetrating network structure was prepared as electrode material of supercapacitor via simple hydrothermal method. When the hydrothermal reaction temperature was 100°C, the MnO2 nanofibers (∼5 nm) were uniformly grown on and within the fluffy 3D porous network of the HPC, forming a composite with interpenetrating network structure. The as-prepared composite (MnO2@HPC-100) exhibited the characteristics of both electric double-layer capacitance and pseudo-capacitance, which had a high specific capacity of 368 F g−1 at a current density of 0.5 A g−1 and 186 F g−1 at 10 A g−1 (50.5% retention). In addition, the asymmetric supercapacitor device was assembled with a relatively high energy density of 88.2 Wh Kg−1 at a power density of 162 W Kg−1. The device had a high capacity retention rate of 95% after 10000 cycles, and the coulomb efficiency was stable at 99.7%, showing the excellent stability of the composite. Therefore, the MnO2@HPC-100 composite has great application prospects in energy storage.