Contact glow discharge electrolysis (CGDE) of acridine orange (AO) was investigated under different mediums, pH, and voltages. The results showed that 500 V was the optimum voltage for CGDE of AO under experimental conditions. The concentration and pH had no appreciable effect on the degradation of AO. Fe2+ had a remarkable catalytic effect on if. From the variation of AO concentration with the reaction time, it was demonstrated that the oxidation would be a first-order reaction. On the grounds of UV spectra of solution in the degradation process, we speculated the intermediate states. The rate constants and relevant coefficiencies were displayed under different conditions.