Concentrations of Al3+ were calculated in soil solutions from concentrations of the monomeric ‘reactive Al’ species ([Al3+] + [Al(OH)2+] + [Al(OH)2+] + [AlF2+]) obtained using a recently reported flow injection analysis (FIA) chelating resin technique. Soil solution samples came from 7 sites encompassing a range of New Zealand soils (Brown, Gley, Pallic, Podzol, and Recent Soils) and vegetation types (pasture, shrub lands, and indigenous and exotic forest). Previously published data from a further 7 sites, obtained using a rapid (7 s) FIA technique, were transformed to give compatible results. The resultant data (n = 85) covered the pH range 2.7–7.6, and showed a single curvilinear relationship for log [Al3+] v. soil solution pH, regardless of vegetation or soil type. At pH >5.6, the data had a slope of –2.98 and fell between the amorphous Al(OH)3 and gibbsite solubility lines. At pH <5.0, the data had a slope of –0.46; further, the soil solutions were under-saturated with respect to both minerals. These results are interpreted as indicating control of Al solubility by Al(OH)3(s) (at pH >5.6) and soil organic matter (at pH <5.0), respectively. This interpretation is supported by data from a pH-dependent Al–fulvic acid binding curve, for which calculated values of [Al3+] follow the same curvilinear relationship determined from the soil solution samples.