The formation of various hydrolytic and mixed hydrolytic complexes of the aluminium(III) ion in the presence of glycine and L‐alanine, has been studied in 0.5 mol dm−3 (Na)NO3 medium at 25deg;C, by emf method. The concentration ratios of amine acids to aluminium(III) were varied from 1 : 1 to 10 : 1. The least‐squares treatment of the data obtained, in the absence of the amino acids, indicates the formation of the dimer, [Al2(OH)2]4+, and monomer, [AlOH]2+, with the stability constants log β22 = −7.03 ± 0.03 and log β11 = −5.65 ± 0.09, respectively. At pH values higher then ∼4.0 formation of the trimer [Al3(OH)4]5+ (log β34 = −12.60 ± 0.08) becomes significant. In the presence of amino acids the evidence has been found for the formation of [Al2(OH)4]2+ (log β24 = −15.65 ± 0.09). Besides the formation of the pure hydrolytic complexes, equilibria in the title systems can be explained by assuming the main reaction products to have the compositions [Al(OH)3Gly] (log β131 = −7.53 ± 0.04), [Al2(OH)2(Gly)2] (log β222 = 6.56 ± 0.09) and [Al(OH)3Ala] (log β131 = −7.70 ± 0.03), [Al2(OH)2Ala2] (log β222 = 7.23 ± 0.07).