Landfill leachate nanofiltration concentrate after ultrafiltration was treated. The experiments were carried out in an electrolytic cell which had an anode chamber and a cathode chamber and could be separated by a proton exchange membrane. Different electrochemical processes combined with peroxydisulfate/Fe3+ (PS/Fe3+) were compared and the reactions in anode chamber and cathode chamber were discussed. The Anode/PS/Fe3+-Cathode/PS/Fe3+ process shows the best effect on COD removal and color removal. The 3D-EEMFS results indicate that Anode/PS/Fe3+-Cathode/PS/Fe3+ process has the best effect on the destruction of organics. In anode chamber, the total COD removal is ascribed to (1) the oxidation by SO4 %-produced from PS activation by original metal ions in the target solution, (2) direct and indirect oxidations by anode, and (3) coagulation caused by Fe3+ after pH adjustment. In cathode chamber, the total COD removal is due to (1) the oxidation by SO4 %produced from PS activation by the regenerated Fe2+ from Fe3+ reduction on cathode, and (2) coagulation caused by Fe3+ after pH adjustment. An optimal experimental condition with current of 80 mA, Fe3+ dosage of 15mM and PS dosage of 37.5mM is obtained for Anode/PS/Fe3+-Cathode/PS/Fe3+ process. The energy consumption between Anode/PS/Fe3+-Cathode/PS/Fe3+ (4.42 kWh/kgCOD) and (Anode+ Cathode)/PS/Fe3+ (4.57 kWh/kgCOD) is similar when 55% of COD is removed. However, the toxicity increase in Anode/PS/Fe3+-Cathode/PS/Fe3+ process is obviously less than that in (Anode+ Cathode)/PS/Fe3+ process.