Electro-Fenton is an efficient approach to degrade refractory organic pollutants in which electro-generated H2O2 are catalyzed by Fe2+ to produce highly reactive hydroxyl radicals ((OH)-O-center dot). The properties of H2O2 formation and recovery of Fe2+ are critical factors in electro-Fenton process, which is related to the electronic structure of catalysts. In this work, the electronic structure of carbon was controlled by incorporation of fluorine (F), which facilitated H2O2 generation and accelerated the recycle of Fe2+ from Fe3+, thus enhancing electro-Fenton activity. The resultant F-doped porous carbon exhibited high H2O2 production rate of 22.4-64.5 mmol L-1 at -0.2 to -0.6 V. The kinetic constant of atrazine degradation achieved 0.10-0.31 min(-1) at potential of -0.2 to -0.6 V. The real secondary effluent of refinery (COD of 92 mg L-1) was successfully treated to meet the National Standard for the Wastewater Discharge of China (COD < 50 mg L-1) with a low specific energy consumption of 6.38 kW h kg(-1) COD-1. This work provides a new insight into design of highly efficient and low-cost catalysts for electro-Fenton treatment of real wastewater.