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In this paper, the effect of electrolyte constituents and metal ions on the discoloration of acid orange 7 (AO) with contact glow discharge electrolysis is investigated. The results indicated that the discoloration rate of AO increased with increasing conductivity of the Na2SO4 solution and then decreased. The discoloration rate of AO was higher in the NaCl solution than in the Na2SO4 solution. Adding a small quantity of ethanol in the solution, the discoloration rate of AO was less than that without it. Cr(VI), Fe2+, and Fe3+ demonstrated apparent enhancing effects on AO discoloration.