To elucidate the dynamics of aluminium (Al), an element potentially toxic and strongly affected by acidification processes, in soils, we selected two regions that were similar in relief, soil types, and vegetation cover but differed markedly in their history of acid precipitation: the Jizerské Mountains (anthropogenically acidified) and the Novohradské Mountains (naturally acidified) in the Czech Republic. The levels of Al forms (exchangeable and organically bound) associated with different environmental impacts were measured and univalent, divalent and trivalent Al species were quantified using HPLC/IC. Exchangeable and organically bound Al concentrations were higher in the anthropogenically acidified area. Only the concentrations of the least-dangerous species, the univalent, in organic soil horizons were similar for both mountains. The concentrations of exchangeable Al forms were correlated with Ca concentrations and with pH in the organic horizon. The known relationship of Al with soil pH was stronger in the mineral horizons. Relationships of exchangeable Al forms concentrations with sulphur concentrations or even more with the sulphur calcium molar ratio were found only in the Jizerské Mountains, not in the Novohradské. Generally, the obtained results support the hypothesis that mechanisms differed between natural and anthropogenic acidification.