The UV photolysis of S2O8(2-) is a novel advanced oxidation technologies (AOTs), which leads to the formation of strong oxidizing radicals, sulfate radicals (SO4(*-)). The effect of oxidant K2S2O8 concentration, the initial pH of solution and various inorganic anions (H2PO4-, HCO3-, NO3- and Cl-) were investigated using AO7, a kind of azo dye, as a model pollutant. The degradation kinetics of AO7 followed pseudo first-order kinetics and reaction rates related to PMS concentrations. When the initial concentration of AO7 was 0.14 mmol/L, the optimal molar ratio of oxidant K2S2O8 to pollutants AO7 was 20. The effect of initial pH had great effect on the AO7 degradation rate during UV/K2S2O8 system. Increasing system pH results in the formation of *OH from SO4(*-). The effects of four inorganic anions (H2PO4-, HCO3-, NO3- and Cl-) all had some negative effect on the degradation of AO7. Based on the results of GC/MS, three main intermediates (2-naphthalenol, coumarin and 1,2-benzenedicarboxylic acid) were identified, thus the degradation pathway for SO4(*-) induced by UV/K2S2O8 was proposed accordingly.