Aluminium mobilization from acidic forest soils in the remote Leigongshan area in southwestern China was investigated in the field and by a laboratory batch experiment using sequential extractions with HCl solutions with pH of approximately 3.4. Experimental data showed that strongly organically bound aluminium (Alp-Alcu) decreased significantly after sequential extraction, whereas exchangeable aluminium (Alex) increased in all three horizons. In the A-horizon with higher base saturation (BS), dissolved aluminium exchanged with base cations (BCs) on soil complex, causing lower aluminium release but significant leaching of BCs. In AB- and B-horizon with lower BS, more dissolved aluminium remained in solution. Al3+ activities in both experimental soil extracts and field soil waters strongly deviated from those predicted by the gibbsite model (i.e., pAl = pKsp + 3.0 pH) despite a significant increase in Al3+ with a decrease in pH. The soil organic-bound aluminium model, using Alcu and Alp to account for differences in the size of available Al pools in the soil, gave considerably better fits to both experimental and field data. SOM-Al model, approved by using Alex instead of organically bound aluminium (i.e., Alp and Alcu), could depict the changes in Al activities most successfully. We have concluded that Alp-Alcu is the main source of aqueous aluminium, whereas Alex plays an important role in regulating aluminium solubility during soil acidification.