This study compared phosphorus (P) speciation and the relationship between bicarbonate extractable (Olsen) P and 0.01 M CaCl2 extractable P (a measure of potentially mobile P) in soils from plots of the Park Grass experiment started in 1856 at IACR-Rothamsted, UK and with and without nitrogen as (NH4)2SO4 and with and without calcium carbonate (CaCO3, lime). A point, termed the change point, was noted in Olsen P, above which 0.01 M CaCl2-P increased at a greater rate per unit increase in Olsen P than below this point. Previous findings have shown a change point for soils with a pH>5.8 at 56 mg Olsen P/kg and at 120 mg Olsen P/kg for soils below this pH. Soils given (NH4)2SO4 annually since 1856 and with lime periodically since 1903 mostly had a pH between 3.7 to 5.7, some of these (NH4)2SO4 treated soils were limed to pH 6.5 and above from 1965. Irrespective of their pH in 1991/92 all the soils had a similar change point (120 mg Olsen P/kg) to that found for other soils with pH<5.8 (112 mg Olsen P/kg). In a laboratory study lasting 30 days, the addition of CaCO3 to acid soils from the field experiment that had received (NH4)2SO4 had a similar change point to soils with pH<5.8 irrespective of pH, suggesting soil P chemistry was controlled by the long period of soil acidity and this was not reversed by a short period at a higher pH. The effect of pH was attributed to the creation of P sorptive surfaces on aluminium precipitates compared with less acidic soils (pH>5.8) where there was less exchangeable Al to be precipitated. This was confirmed with solid-state 31P nuclear magnetic resonance, which indicated that for soils of similar total P concentration and pH, there was twice as much amorphous Al-P in soils given (NH4)2SO4 compared with those without. Changes in pH as a result of applications of (NH4)2SO4 or lime can greatly change the concentration of potentially mobile P due to the effects on Al solubility. Although there was less potentially mobile P in soils with pH<5.8 than in soils above this pH, it is usually advised in temperate regions to maintain soils about pH 6.5 for arable crops.