Abstract: To explore the treatment effect of electro catalysis and Fenton technology on the advanced treament of leachate, chemical oxidation by electro catalytic/Fenton (EF)to deal with transfer leachate had been optimized using orthogonal experimental design. The variables considered were voltage, HRT, H₂O₂/COD₀ and H₂O₂/Fe²⁺ molar ratio. Then the molar ratios of H₂O₂ and COD₀, H₂O₂ and Fe²⁺ were studied in detail. Furthermore, the activated carbon fiber (ACF)/cathode area ratio was studied to show the effect of ACF on the COD removal. Results show that voltage has the largest effect on COD removal ratio. The optimum operating conditions are decided as voltage of 5.5 V, HRT of 50 min, H₂O₂ and COD₀ molar ratio of 1.2, H₂O₂ and Fe²⁺ molar ratio of 2.0. When the area ratio of ACF and cathode is 1:2, the COD decreases at most. The degradation pathway of COD in leachate using electro catalytic/Fenton is obtained by the comparative experiments of adsorption, Fenton, electrolytic and electro catalytic/Fenton.