The peroxone process (O3/H2O2) is reported to be a more effective process than the ozonation process due to an increased rate of generation of hydroxyl radicals (•OH) and inhibition of bromate (BrO3−) formation which is otherwise formed on ozonation of bromide containing waters. However, the trade-off between the H2O2 dosage required for minimization of BrO3− formation and effective pollutant removal has not been clearly delineated. In this study, employing experimental investigations as well as chemical modelling, we show that the concentration of H2O2 required to achieve maximum pollutant removal may not be the same as that required for minimization of BrO3− formation. At the H2O2 dosage required to minimize BrO3− formation (<10 µg/L), only pollutants with high to moderate reactivity towards O3 and •OH are effectively removed. For pollutants with low reactivity towards O3/•OH, high O3 (O3:DOC>>1 g/g) and high H2O2 dosages (O3:H2O2 ∼1 (g/g)) are required for minimizing BrO3− formation along with effective pollutant removal which may result in a very high residual of H2O2 in the effluent, causing secondary pollution. On balance, we conclude that the peroxone process is not effective for the removal of low reactivity micropollutants if minimization of BrO3− formation is also required.