The technology of direct reduction by adding sodium carbonate (Na2CO3 ) and magnetic separation was developed to treat Western Australian high phosphorus iron ore. The iron ore and reduced product were investigated by optical microscopy and scanning electron microscopy. It is found that phosphorus exists within limonite in the form of solid solution, which cannot be removed through traditional ways. During reduction roasting, Na2CO3 reacts with gangue minerals (SiO2 and Al2O3 ), forming aluminum silicate-containing phosphorus and damaging the ore structure, which promotes the separation between iron and phosphorus during magnetic separation. Meanwhile, Na2CO3 also improves the growth of iron grains, increasing the iron grade and iron recovery. The iron concentrate, assaying 94.12wt% Fe and 0.07wt% P at the iron recovery of 96.83% and the dephosphorization rate of 74.08%, is obtained under the optimum conditions. The final product (metal iron powder) after briquetting can be used as the burden for steelmaking by an electric arc furnace to replace scrap steel. The technology of direct reduction by adding sodium carbonate (Na2CO3) and magnetic separation was developed to Western Australian high phosphorus iron ore. The iron ore and reduced product were investigated by optical microscopy and scanning electron microscopy. It is found that phosphorus exists within limonite During reduction roasting, Na2CO3 reacts with gangue minerals (SiO2 and Al2O3), forming aluminum silicate-containing phosphorus and damaging the ore structure, which promotes the separation between iron and phosphorus The iron concentrate, assaying 94.12 wt% Fe and 0.07 wt% P at the iron recovery of 96.83% and the dephosphorization rate of 74.08 %, is obtained under the optimum conditions. The final product (metal iron powder) after briquetting can be used as the burden for steelmaking by an electric arc furnace to replace scrap steel.