Hydrolysis of aluminum(III) ion in 3.0 M (Na)NO3 medium was studied by emf method at 25° C. Data cover the range 1–78 mM Al(III) within the pH range of 2.0–4.5. At a definite pH, the extent of hydrolysis increases with increasing aluminium concentration, thereby indicating the presence of polynuclear hydrolysis products. The least squares treatment of the data indicates the formation of polynuclear hydrolytic complexes [Formula: see text] [Formula: see text] and [Formula: see text] With the reactions written in the form[Formula: see text]the stability constants obtained were log (β2,2 = −7.55 ± 0.21, log β2,4 = −16.41 ± 0.13, and log (β3,4 = −13.24 ± 0.08. Distribution curves indicate that the complex [Formula: see text] is predominant. Key words: hydrolysis, aluminum(III) ion, hydrolytic complexes, aluminum(III) ion hydrolysis.