Several Al-substituted goethites were synthesized by hydrolysis of Fe3+ salt solutions. The kinetics of the reductive dissolution of these goethites in dithionite-ethylenediaminetetraacetic acid (D-EDTA) was studied at pH 5.5, at 303, 323 and 333 K. The initial dissolution rate (R) per unit of surface area decreases with Al substitution. In the sample with greater Al content (G″7), the kinetic profiles of the dissolved Fe fraction vs. time gave a small positive intercept. The kinetic profile of R as a function of EDTA initial concentration shows a significant weakening in the presence of Al. The maximum is flatter and wider in Al-substituted goethite than that of pure goethite. In sample G″7, where the Al content is 11.3 mol.% the maximum is obtained when the [D]:[EDTA] initial ratio is ~4.5 vs. 2 in un-substituted goethite. These results can be attributed to the lesser density of the more active dimeric sites, the presence of more strongly bonded Al–O–Fe with regard to Fe–O and the small value for the ≡Al-EDTA surface species constant. Activation energy (Ea) increases with Al substitution. Its value is doubled from G0 (pure goethite) to G″7 (11.3 mol.% of Al). The frequency factor (A) acts in the opposite sense to Ea, but it is not sufficient to outweigh the effect of Ea.