Two diaphragm electrolysis systems, two-electrode (anode–cathode) and three-electrode (cathode–anode–cathode), were compared for the electrochemical degradation of 4-chlorophenol. The performance of these systems was improved by feeding with hydrogen gas and then with air, in aid of the combined processes of reduction and oxidation. The 4-chlorophenol degradation, dechlorination, and total organic carbon removal were monitored to characterize the difference between the two systems. The results indicated that the three-electrode system exhibited higher degradation percentages for 4-chlorophenol compared with that of the two-electrode system. The dechlorination property of the three-electrode system was stronger than that of the two-electrode system. In addition, the total organic carbon removal percentage of the anodic compartment in the three-electrode system was higher than that of the two-electrode system. The three-electrode system showed excellent treatment properties for 4-chlorophenol.