In an aqueous solution, normal electrolysis at high voltages switches over spontaneously to glow discharge electrolysis and gives rise to hydroxyl radical, hydrogen peroxide, and aqueous electron, as well as several other active species. Hydroxyl radical directly attacks organic contaminants to make them oxidized. In the present paper, 2-naphthylamine is eventually degraded into hydrogen carbonate and carbon dioxide. The degradation process is analyzed by using an Ultraviolet (UV) absorption spectrum, high-performance liquid chromatography (HPLC) and chemical oxygen demand (COD). It is demonstrated that 2-naphthylamine (c0 =30 mg·l-1) is completely converted within 2h at 30°C and 600 V by glow discharge electrolysis, and the degradation is strongly dependent upon the presence of ferrous ions. COD is ascended in the absence of ferrous ions and descended in the presence of them.