In this work, the response surface methodology (RSM) was used to model and optimize the hydroxylamine (HA) enhanced Fe(II)/peroxymonosulfate (PMS) process. The enhanced effect of HA on the degradation efficiency of Orange II (AO7) in the Fe(II)/PMS system was quantitatively analyzed. Pareto analysis showed that the individual and interactive effects of HA, Fe(II) and PMS were of the following order: HA > Fe(II) > PMS and Fe(II)/PMS > HA/PMS > Fe(II)/HA. The optimal conditions of HA/Fe(II)/PMS system were as follows: Fe(II) concentration was 34.0 μM, HA concentration was 0.4 mM, and PMS concentration was 0.9 mM. When the initial pH was 4.0-6.0, the degradation efficiency of AO7 in the HA/Fe(II)/PMS system was significantly higher than that in the Fe(II)/PMS system (P < 0.05). Hydroxylamine enhances the degradation of AO7 in the Fe(II)/PMS system by reducing Fe(III) to Fe(II). The results of quenching experiment showed that SO4•- was the dominating reactive oxygen species (ROS) in the HA/Fe(II)/PMS system. In the HA/Fe(II)/PMS system, CO32- and humic acid inhibited the degradation efficiency of AO7. This work provides a novel mathematical model for the degradation of AO7 in the HA/Fe(II)/PMS system, which can be popularized and applied in similar experiments.