SUMMARYEleven horizons of acidic soils developed from Lower Palaeozoic sedimentary rocks in mid Wales contained varying amounts of poorly ordered minerals. In nine of these over 70% of the phosphate adsorption capacity was attributed to poorly ordered minerals. Iron oxide with substituted Al, and a separate Al oxide, together accounted for the phosphate adsorption of the poorly ordered fraction. Aluminium‐substitution had no major effect on the adsorption capacity of Fe oxide, but since Al occurred in both active minerals it masked the effect of Fe on phosphate adsorption in simple correlations. The relative contribution of the two mineral forms to phosphate adsorption varied widely between soils. Aluminium as a substituent in Fe oxide and in ‘free’ oxide form was responsible for the soils’ reactivity towards NaF, but no distinction could be made between these poorly ordered forms. For certain horizons both poorly ordered Al and Si were correlated with OH−release, but Al oxides were more important than