Abstract: Although the existing coking wastewater treatment technology can make the final discharge wastewater meet the national standard of China,the effluent COD from more than 90% of coking wastewater treatment during actual operation cannot really meet the standard. The high removal cost of refractory organic pollutants is one of the main reasons. In order to coordinately solve both problems of high cost and low efficiency of organic matter and the poor settlement of coal particles with small size in coking wastewater treatment,a Fe(〖KG-*5〗Ⅵ)/H2O2 system was established,by combining the advantages of both the Fe(〖KG-*5〗Ⅵ)oxidation method and Fenton like method,and the flocculability of the reaction product Fe(Ⅲ)together,to investigate the rapid oxidation flocculation effect of coal particles in aqueous solution,and collaborative removal of coal particles and organic matter in the actual coking wastewater by the Fe(〖KG-*5〗Ⅵ)/H2O2system,in order to provide an important theoretical basis for the further development of coking wastewater treatment technology with high efficiency and low consumption. The Zeta potential value on the particle surface was selected as the main index reflecting the settling property of coal particles,and the single-factor experiment was used to investigate the effects of the addition amount of H2O2,the reaction time of Fe(〖KG-*5〗Ⅵ)and H2O2,respectively,and inorganic salts on the oxidized coal particles by Fe(〖KG-*5〗Ⅵ)/H2O2 system. The actual coking wastewater was collected,and the synergism effect of Fe(〖KG-*5〗Ⅵ)/H2O2 system on COD,ammonia nitrogen and SS was studied. The results showed that Fe(〖KG-*5〗Ⅵ)and H2O2 could form complementary advantages,which improved the flocculation and settlement performance of coal particles to some extent. After coal particles oxidized by Fe(〖KG-*5〗Ⅵ)for 40 s,H2O2 was added to react for another 15 min,and then,the absolute value of Zeta potential on the surface of coal particles decreased significantly,achieving a better flocculation and settlement effect. Inorganic cations could compress the double electric layers on the surface of coal particles,thus reducing the absolute Zeta potential and improving the settlement of coal particles. After using Fe(〖KG-*5〗Ⅵ)/H2O2 system to treat actual coking wastewater,the removal rates of COD,ammonia nitrogen and SS reached 69.27%,75.95% and 89.81%,respectively,with certain decolorization effect.