Functionalized three-dimensional hierarchical porous carbon (THPC) is prepared via a facile modified chemical activation route with polypyrrole microsheets as precursor and KOH as activating agent. The as-obtained THPC presents a large specific surface area (2870 m² g⁻¹), high-level heteroatom doping (N: 7.7 wt%, O: 12.4 wt%), excellent electrical conductivity (5.6 S cm⁻¹), and hierarchical porous nano-architecture containing macroporous frameworks, mesoporous walls and microporous textures. Such unique features make the THPC an ideal electrode material for electrochemical energy storage. As the electrode material for a supercapacitor, the THPC exhibits a high capacitance, excellent rate performance and long-term stability in both aqueous and organic electrolytes.