The performance of gas diffusion electrodes in electrochemical benzene hydrogenation is discussed. The effects of electrode preparation conditions, electrolyte acidity, reaction temperature, benzene and vapor concentration, and N₂ fluid rate are investigated by evaluating the efficiency of current and the reaction rate. The results of the experiment show that gas diffusion electrodes with 10% (wt) PTFE and 0.75 mg/cm² Nafion content could attain a high efficiency of current (35%) under optimal operating conditions. The optimal operating conditions were as follows: temperature of electrolysis 70 °C, electrolyte acidity 1 mol/L H⁺, benzene concentration 26%, vapor concentration 10%, and N2 fluid rate between 80 mL/min and 240 mL/min. Electrodes modified by polyethylene glycol (PEG6000) of 0.20%(wt) efficiently reduced the resistance of transference mass and improved the rate of the hydrogenation reaction.