SUMMARYIron oxides from 39 soils derived from various parent materials in south‐western Australia have been studied using a variety of techniques. Goethite and hematite were the only two Fe oxides present. The goethite/(goethite+hematite) ratio ranged from 0.18 to 1.0, and was highest in soils on acidic igneous rocks, decreasing for soils on alluvial and mafic parent materials. In a few soils derived from acid rocks only goethite was present. The redness rating of soils increased linearly with increasing amount of hematite. Al substitution in goethite ranged from 13 to 35 mol%, with higher values for soils on acid igneous rocks (median value = 26 mol%) than for soils on mafic (19 mol%) and alluvial (17 mol%) parent materials. Substitution of A1 in hematite ranged from 4 to 23 mol%, and was greatest in soils on mafic parent materials (median value = 12 mol% A1). A1 substitution in hematite was about half of that in associated goethite. The dehydroxylation temperature for goethite increased linearly with increasing A1 substitution. Goethite and hematite had similar crystal sizes (c. 20 nm), and both were in the form of irregular plates.Dissolution with 1 M HCl of iron oxides concentrated from the soils by 5 M NaOH digestion could be described both by the Cube Root Law and by Kabai's equation. Only one straight line was obtained for the dissolution data using Kabai's equation for samples containing both goethite and hematite, in contrast to the results of other workers. Major proportions of the Co, Cr, Cu, Mn, Ni and Zn in the soils were concentrated with the iron oxides, and the dissolution kinetics of these elements indicate that some may be present in the structure of the iron oxide