The various mechanisms by which phosphorus (P) occurs and is distributed within banded iron formations (BIF)-derived iron ore are examined. In unenriched, precursor BIF P occurs predominantly as discrete grains of primary apatite. In high-grade ores hosted mainly by the Brockman Iron Formation, P occurs in three main forms:1. as secondary apatite;2. other submicron, P-rich phases (eg Rare earth containing minerals (REE), vivianite, strengite,wavellite) present in pore networks; and3. as P occurring with iron oxides, in particular, goethite.However, the presence of secondary P-bearing phases does not contribute signifi cantly to the total P level in iron ore, and it is P associated mainly with goethite, which represents the most common occurrence of P in these ores.No direct evidence for the replacement of Fe by P within the structure of synthetic goethite has been demonstrated. Therefore, it is most likely that in iron ores P associates with goethite in occluded form as adsorbed PO4 3- species or as discrete P-bearing minerals, such as strengite, wavellite or vivianite, in ultra-fine, micro-pores or within intra-domain regions of multi-domainic goethite. Such occluded P is not easily extracted with commonly used lixiviants, such as weakly alkaline leachates. Recent development of a low temperature-alkalie/water leach extraction method has been successful in reducing not only the P content, but also amounts of Si and Al inthe initial ore. Refi nement of such a method to commercial application will have enormous benefit in realising the economic potential of large tonnages of high-P (ie >0.07 wt per cent P) bearing iron ore.