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The decolorization of methyl orange wastewater by DC stream discharge with MgO-CuO-Al2O3 catalyst was investigated. The removal efficiency was studied for different experimental parameters. Results showed that the removal efficiency by discharge with catalyst was better than discharge only. The removal efficiency was 98% under the condition of applied voltage 18kV, current 9mA, volume of catalyst 20cm3, initial concentration 40mg/L with treatment for 10min. The intensity of methyl orange absorption peak (465nm) gradually weakened and disappeared by discharge with catalyst, the conjugated system composed of azo group and benzene in the molecular structure was destroyed, methyl orange molecules were degraded effectively.