Electrochemistry coupled with granulated activated carbon catalysis of peroxymonosulfate (electro/GAC/PMS) as a novel wastewater treatment process was performed for the degradation of Acid Orange 7 (AO7) in aqueous solution. The decolorization of AO7 was compared under different permutations and combinations of electro-oxidation, GAC and PMS. It showed that the electro/GAC/PMS process was the most effective and the decolorization of AO7 followed pseudo-first order kinetics. The surface chemistry of GAC samples was analyzed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Compared with the fresh samples, π-electron density and hydroxyl group content decreased under the GAC/PMS system, but kept the similar values under the electro/GAC/PMS system. Electron paramagnetic resonance and radical scavenger studies were used to verify the formation of sulfate radicals (SO4-) and hydroxyl radicals (OH). The optimized conditions were found to be: current density 8 mA cm-2; PMS concentration 5 mM; GAC dosage 0.5 g L-1; and initial pH value 5.0. GAC recycling experiments over 4 runs showed some decrease in reactivity. Overall, the results indicate that 100% color removal was readily achieved and 50.4% of TOC was removed which shows high efficiency of the electro/GAC/PMS process.