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Gas diffusion electrodes are applied to the coupled reaction of water electrolysis and electrocatalytic benzene hydrogenation. The effects of the preparation conditions of electrodes, electrolyte acidity, the concentration of benzene and water vapor, and the flow rate of N2 are investigated by evaluating the efficiency of the current. Furthermore, the optimal operational conditions have been ascertained. The results of our experiment show that gas diffusion electrodes have good performance when the content of PTFE is 10% (wt) and that of Nafion is 0.75mg/cm2. The optimal operational conditions are as follows: The temperature of electrolysis is 70℃, acidity 0.5mol/L, the concentration of benzene 26%,the concentration of vapor 10%, the flow rate of N2 80mL/min-240mL/min. The efficiency of the current can reach 35%under optimal operational conditions. Then, a conclusion can be drawn that gas diffusion electrodes can improve the rate of the coupled reaction effectively.