Hematite exists ubiquitously in soils and sediments, and is commonly aluminium (Al)-substituted. This study investigated systematically the effects of Al substitution on the visible diffuse reflectance spectrum (DRS) of hematite by using several sets of synthetic samples. We found that the position and amplitude of the characteristic absorption band of hematite (estimated from the first- and second-order derivative curves of the Kubelka-Munk remission function spectrum derived from the DRS) was significantly affected by the degree of Al substitution as well as by sample grain morphology. Therefore, there are ambiguities in quantifying the degree of Al substitution and the mass concentration of hematite using DRS. Nevertheless, if hematite forms under similar environmental conditions, it is possible to establish a transfer function between the DRS parameters and hematite concentration as discussed here for a Chinese loess-palaeosol sequence.