Abstract: In order to improve the electricity generation performance and membrane anti-fouling properties, the Co-NPs/PVDF carbon fiber catalytic membrane was prepared by using metal-organic frameworks (MOFs) as precursor to prepare nitrogen-doped carbon with supported Co nanocatalysts (Co-NPs) for high oxygen reduction reaction (ORR) catalytic activity through high-temperature carbonization, and carbon fiber cloth as the matrix. The catalytic membrane coupled EMBR system was constructed to treat the actual coking wastewater. The effects of carbonization temperature, Co/N synergistic action, N-doped content and speciation on ORR activity were investigated. The pollutant removal efficiency, anti-fouling characteristics and efficiency of electricity production in EMBR treatment of coking wastewater were explored. The results showed that the ORR reaction of Co-NPs was 4 electron transfer reduction pathway and the reduced product was water. The Co-NPs/PVDF carbon fiber catalytic membrane can maintain a high stable membrane flux under the microelectric field. In the early stage, the catalytic fouling conformed to the membrane hole plugging model. While, in the later stage, the membrane fouling was controlled by the filter cake fouling model and the membrane fouling was mainly the contamination of the filter cake layer. The micro-electric field can reduce the specific resistance of the membrane filter cake layer and effectively solve the problem of membrane fouling. The EMBR system treated the actual coking wastewater and the degradation rates of COD, TN, NH₄⁺-N and volatile phenol were 97.2%, 43.8%, 82.9% and 99.8%, respectively. The maximum electrical power density of the EMBR was 823.8 mW/m³ and the coulomb efficiency was about 8.3%. The results indicated that the Co-NPs/PVDF carbon fiber catalytic membrane that was prepared by using metal-organic frameworks (MOFs) as precursor to prepare Co-NPs and carbon fiber cloth as the matrix and coupled EMBR system had shown high pollutant degradation efficiency and energy conversion efficiency in the coking wastewater treatment, and the micro-electric field can achieve the effect of membrane anti-fouling.