The feasibility of dephosphorization using the flotation process and its mechanism of high-phosphorus oolitic hematite were discussed in this paper. The results showed that phosphorus minerals mainly exist in the form of collophane, which can be divided into three types. Block collophane and band collophane could be effectively removed through flotation, while the third type could not be eliminated through physical concentration alone. A lab-made fatty acid was identified as an effective collector for high-phosphorus oolitic hematite, resulting in a product containing 57.67% iron and 0.14% phosphorus with a flotation recovery rate of 82.43%. The study of the flotation mechanism revealed that, in the presence of starch and the lab-made fatty acid, there was both physical absorption and chemisorption occurring on the surfaces of apatite. However, only very weak physical absorption was observed on the surface of hematite.