The efficient development and utilization of high-phosphorus oolitic hematite is of great strategic significance for the sustainable supply of iron-ore resources in China. In this paper, the mechanism of high-temperature pretreatment for enhancing the effect of iron enrichment and dephosphorization in the magnetization roasting-leaching process was studied by X-ray diffraction (XRD), vibration sample magnetometer (VSM), scanning electron microscopy and energy dispersive spectrometry (SEM-EDS). Compared with the process without high-temperature pretreatment, the iron grade of the magnetic separation concentrate after high-temperature pretreatment had increased by 0.98%, iron recovery rate had increased by 1.33%, and the phosphorus content in the leached residue had decreased by 0.12%. High-temperature pretreatment resulted in the dehydration and decomposition of hydroxyapatite, the dehydration of limonite and the thermal decomposition of siderite, which can produce pores and cracks and weaken the compactness of the ore, improve the magnetization characteristics of roasted ore, and strengthen the iron enrichment and dephosphorization during the magnetization roasting and leaching process.