In this study, a high-phosphorus oolitic iron ore containing 44.70% Fe and 1.56% P from western Hubei of China was collected as the sample. The chemical composition, mineral composition, structure characteristics, dissemination characteristics, and iron and phosphorus occurrence state were carried out to investigate the mineralogical characteristics of the high-phosphorus oolitic iron. The results show that the high-phosphorus oolitic iron ore is a chemical sedimentary iron ore, mainly composed of oolite (more than 60%). Specifically, the ooids consists of oolite nuclei, collophanite girdles, and hematite and limonite girdles; the detritus is composed of fine-grained hematite and quartz feldspar; and cement is composed of carbonate minerals and worm-like hematite. The iron concentrate consists of iron-rich oolite and some hematite. The iron-bearing minerals in the oolite are mainly hematite, limonite, chlorite, and collophanite, and a close relationship between the hematite-limonite in the oolites and the iron-containing chamoisite can be observed. Upgrading iron and removing phosphorus from the high-phosphorus oolitic iron ore will be difficult by physical beneficiation.