Freestanding hierarchically porous carbon electrode materials with favorable features of large surface areas, hierarchical porosity and continuous conducting pathways are very attractive for practical applications in electrochemical devices. Herein, three-dimensional freestanding hierarchically porous carbon (HPC) materials have been fabricated successfully mainly by the facile phase separation method. In order to further improve the energy storage ability, polyaniline (PANI) with high pseudocapacitance has been decorated on HPC through in situ chemical polymerization of aniline monomers. Benefiting from the synergistic effects between HPC and PANI, the resulting HPC/PANI composites as electrode materials present dramatic electrochemical performance with high specific capacitance up to 290 Fg(-1) at 0.5 Ag-1 and good rate capability with similar to 86% (248 Fg(-1)) capacitance retention at 64 A g(-1) of initial capacitance in three-electrode configuration. Moreover, the as-assembled symmetric supercapacitor based on HPC/PANI composites also demonstrates good capacitive properties with high energy density of 9.6 Wh kg(-1) at 223 W kg(-1) and long-term cycling stability with 78% capacitance retention after 10 000 cycles. Therefore, this work provides a new approach for designing high-performance electrodes with exceptional electrochemical performance, which are very promising for practical application in the energy storage field. (C) 2016 Elsevier B.V. All rights reserved.