We investigated the removal effects of chloride ion on treating organic substances with electrolysis using leachate from semiaerobic bioreactors. The experimental results show that, under the given conditions, the removal efficiency of refractory organic substances increases with rising initial chloride ion concentration in leachate. The impact of chloride ion on removal efficiency mainly is influenced by the initial chloride ion concentration and the chemical oxygen demand (COD) in leachate. The impact of chloride ion on the specific electric consumption of removal COD is obvious when the initial chloride ion concentration is lower. No obvious change of this impact is observed when the chloride ion concentration exceeds 125 g/L. Meanwhile, the more obvious impact of initial chloride ion concentration on organic substance removal is observed when the COD concentration in leachate is lower.