<p>The developed technology for the active carbon with controlled hierarchical porosity structure is a key strategy for the advanced electrode materials in electric double layer capacitors (EDLCs). Herein, the newly prepared method for the porous carbon was developed by using the corn starch as a biomass carbon precursor to prepare primary porous carbon materials, and then it suffered from the secondary adjustment of pore structure by using small molecule glucose as regulator. With suitable feeding ratio of primary carbon and glucose, the prepared porous carbon exhibited the rich microporous structure and the improved specific surface area, which, as the electrode material of EDLCs, exhibited the improved specific capacitance and rate performance. As the feeding mass ratio of carbon and glucose was 20:1, the secondary-carbonized porous carbon (GACR-20) in three electrode system exhibited an improved specific capacitance of 257 F g⁻¹ at 0.5 A g⁻¹, with a 28% increase as compared to the primary porous carbon materials (ACR) (200 F g⁻¹). In two electrode system, GACR-20 exhibited the largest specific capacitance of 175 F g⁻¹ at 0.5 A g⁻¹ and 153 F g⁻¹ even at high current density of 10 A g⁻¹. Also, it still maintained 83% of capacitance retention even after 10,000 cycles at 2 A g⁻¹. And its highest power density at 10 A g⁻¹ reached 2500 W kg⁻¹ with the corresponding energy density of 10.6 Wh kg⁻¹. The work has certain reference significance for the preparation of advanced activated carbon as the electrode materials of EDLCs.</p>