The oxidation of diclofenac (DCF), a non-steroidal anti-inflammatory drug and emerging water pollutant, with chlorine dioxide was investigated under simulated water disinfection conditions. The reaction kinetics as functions of the initial concentrations of DCF, different nitrogenous species, and different pE values were experimentally determined. The results demonstrated that DCF reacted rapidly with ClO2, where more than 75 % of DCF (≤3.00 μM) was removed by 18.94 μM ClO2 within 60 s. All of the reactions followed pseudo first-order kinetics with respect to DCF, and the rate constant, k obs, exhibited a significant decrease from 4.21 × 10(-2) to 8.09 × 10(-3) s(-1), as the initial DCF concentration was increased from 1.00 to 5.00 μM. Furthermore, the degradation kinetics of DCF was clearly dependent on nitrogen-containing ion concentrations in the reaction solution. Ammonium and nitrite ions inhibited the DCF degradation by ClO2, whereas nitrate ion clearly initiated its promotion. In contrast, the inhibitory effect of NO2 (-) was more robust than that of NH4 (+). When the values of pE were gradually increased, the transformation of NH4 (+) to NO2 (-), and subsequently to NO3 (-), would occur, the rate constants were initially decreased, and then increased. When NH4 (+) and NO2 (-) coexisted, the inhibitory effect on the DCF degradation was less than the sum of the partial inhibitory effect. However, when NO2 (-) and NO3 (-) coexisted, the actual inhibition rate was greater than the theoretical estimate. These results indicated that the interaction of NH4 (+) and NO2 (-) was antagonistic, while the coexistence of NO2 (-) and NO3 (-) was observed to have a synergistic effect in aqueous environments.