In this study, an electrochemical system was established for simultaneous harmless removal of nitrate and ammonia multiple contamination in an undivided single cell. Cyclic voltammetry was used to investigate the electrochemical cathode and anode coupling redox mechanism and concurring evolution of nitrate and ammonia. The cyclic voltammograms showed the cathodic reduction of nitrate to ammonia and nitrite, the chloride ion conversion to hypochlorite and hypochlorous acid, and the oxidation of ammonia to nitrogen gas and nitrate. A circular transformation process was formed in the electrochemical system and the final product was harmless nitrogen gas. The multiple nitrogen pollutants in the original contaminated system were gradually removed with the reaction predominantly produced harmless nitrogen gas. Response surface methodology was used to build mathematical models for optimizing the operating conditions. The optimum time, NaCl concentration, and current density were 85.38 min, 0.24 g/L, and 45.13 mA/cm(2), respectively. Under the optimum conditions, the nitrate and ammonia concentrations in the treated solution were 9.17 and 0.00 mg/L, respectively.