The direct reduction–magnetic separation process based on coal is considered to be one of the most important methods that can effectively utilize high-phosphorus oolitic hematite. In this study, the mechanism of the effects of CaCO<sub>3</sub> and Na<sub>2</sub>CO<sub>3</sub> on the dephosphorization of high-phosphorus oolitic hematite during the direct reduction process was investigated using X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectrometer (EDS). The results showed that Na2CO3 and CaCO3 reacted with Al<sub>2</sub>O<sub>3</sub> and SiO<sub>2</sub> during the direct reduction process, inhibited the generation of hercunite (FeAl<sub>2</sub>O<sub>4</sub>) and fayalite (Fe<sub>2</sub>SiO<sub>4</sub>), and promoted the reduction of metallic iron (Fe). Furthermore, the reaction inhibited the reduction of apatite and prevented the generation of FeP<sub>2</sub>. Na<sub>2</sub>CO<sub>3</sub> could change the form of phosphorus in the gangue from Ca<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> to Na<sub>2</sub>Ca<sub>4</sub>(PO<sub>4</sub>)<sub>2</sub>SiO<sub>4</sub>. Increasing the dosages of Na2CO3 and CaCO3 in the dephosphorization agent and increasing the content of Na<sub>2</sub>CO<sub>3</sub> in the dephosphorization agent were beneficial to the growth of metallic iron particles, and increasing the dosage of Na<sub>2</sub>CO<sub>3</sub>, CaCO<sub>3</sub> in the dephosphorization agent had more significant effects on metallic iron particles than increasing the content of Na<sub>2</sub>CO<sub>3</sub> in the dephosphorization agent. The research conducted in this study is expected to provide a basis for the effective exploitation of complex and refractory iron ores.