A novel strategy is proposed for the increase of specific surface area (SSA) of porous carbon sphere (PCS) by oxidation and activation. 2-keto-l-gulonic acid mother liquor (GAML) as a high-pollution waste has a relatively high value of reutilization. For its high value-added utilization, GAML is used as the precursor for preparation of PCS as carbon-based electrode materials for electric double-layer capacitor. PCS is prepared by hydrothermal carbonization, carbonization and KOH activation, and Fe(NO3)3 9H2O is used as an oxidizing agent during carbonization. The as-prepared PCS has excellent porosity and high SSA of 2478 m2 g-1. Meanwhile, the pore structure of PCS can be controlled by the adjustment of carbonization parameters (carbonization temperature and the loading of Fe(NO3)3 9H2O). Besides, the SSA and specific capacitance of PCS can be increased remarkably when Fe(NO3)3 9H2O is added in carbonization. The specific capacitance of PCS can reach 303.7 F g-1 at 40 mA g-1. PCSs as electrode material have superior electrochemical stability. After 8000 cycles, the capacitance retention is 98.3% at 2 A g-1. The electric double-layer capacitance of PCS is improved when CS is carbonized with Fe(NO3)3 9H2O, and the economic and environmental benefits are achieved by the effective recycle of GAML.