A hybrid electrolytic water system was constructed including the anodic electro-oxidation treatment of the leachate from a waste incineration plant as well as the coupled cathodic electrolysis for hydrogen production. Four types of electrolyzers were designed with different flow channels and investigated the effect of different electrolysis parameters on the coupled reactions. The results indicate that the pin-type electrolyzer is superior to the other three electrolyzers in term of the degradation performance and energy consumption. At high current density of 4000 A/m2 and the flow rate of 100 ml/min, the pin-type electrolyzer shows the lowest potential of 6.09 V, the COD removal rate of 98.17% for the leachate and the energy consumption of 200.14 W h. The mass transfer mechanism was further explored under different flow channels and current densities, illustrating that the excellent performance of the pin-type electrolyzer is due to its largest mass transfer area and the most uniform inside flow field distribution. The apparent COD degradation kinetic behaviors were studied, indicating that the maximum degradation rate was 0.033 min-1 at the electric density of 4000A/m2. Such electrocatalytic oxidation of waste leachate coupled with hydrogen production would provide a promising route to construct new hybrid electrolytic water systems.