Abstract: The effect of CaCO₃, Na₂CO₃, and CaF₂ on the reduction roasting and magnetic separation of high-phosphorus iron ore containing phosphorus in the form of Fe₃PO₇ and apatite was investigated. The results revealed that Na₂CO₃ had the most significant effect on iron recovery and dephosphorization, followed by CaCO₃, the effect of CaF₂ was negligible. The mechanisms of CaCO₃, Na₂CO₃, and CaF₂ were investigated using X-ray diffraction (XRD), scanning electron microscopy and energy dispersive spectrometry (SEM–EDS). Without additives, Fe₃PO₇ was reduced to elemental phosphorus and formed an iron–phosphorus alloy with metallic iron. The addition of CaCO₃ reacted with Fe₃PO₇ to generate an enormous amount of Ca₃(PO₄)₂ and promoted the reduction of iron oxides. However, the growth of iron particles was inhibited. With the addition of Na₂CO₃, the phosphorus in Fe₃PO₇ migrated to nepheline and Na₂CO₃ improved the reduction of iron oxides and growth of iron particles. Therefore, the recovery of iron and the separation of iron and phosphorus were the best. In contrast, CaF₂ reacted with Fe₃PO₇ to form fine Ca₃(PO₄)₂ particles scattered around the iron particles, making the separation of iron and phosphorus difficult.