In this study, peroxymonosulfate (PMS) was activated by cheap and readily available natural iron ore to remove Acid Orange 7 (AO7) in water with the assistance of hydroxylamine (HA). Results show that the presence of HA could accelerate the Fe(II)/Fe(III) cycle on the ore surface, promoting the activation of PMS to generate reactive oxidative species. The effects of ore dosage, PMS dosage, HA dosage and initial pH on the degradation of AO7 were investigated in the HA/Ore/PMS system. Under the optimal conditions, the removal of AO7 could reach 93.1% during 30 min, which was 41.4% higher than the ore/PMS system. The AO7 removal increased with the increase of HA, PMS and ore dosage, but was unaffected by the initial solution pH. Based on radical scavenging experiments and EPR tests, the dominant reactive species in the HA/Ore/PMS system were revealed to be the sulfate radical (SO₄^•−), singlet oxygen (¹O₂), superoxide radical (O₂^•−) and hydroxyl radical (^•OH), which were responsible for the AO7 degradation. Furthermore, the possible reaction mechanism of PMS activation was proposed. This study provides an efficient technique for the removal of azo dye organic contaminant in water, which has great practical significance.