A kind of micro-meso hierarchical porous carbon (HPC) was prepared by a combination of organic-organic self-assembly approach and post-activation approach, and also investigated as an electrode material in electrochemical capacitors. Pore structure analysis shows that micropores can be adjustably generated on the mesopore wall of mesoporous carbon (MC) by post activation at high temperature using KOH as an activating agent. As evidenced by electrochemical measurements, HPC shows superior capacitive behavior (exhibiting a high capacitance of up to 168.9 F/g even at a very high sweep rate of 100 mV/s) to hard-templated carbon reported in the literature. Of special interest is the fact that HPC has very excellent capacitance at high frequency of 1 Hz, reaching up to 180 F/g that is the highest value than any other electrode material reported in the literature. The excellent capacitive performance of HPC can be ascribed to its unique hierarchical porous structure that favors the fast diffusion of electrolyte ions in its pore structure.