The hydrolysis of gallium(III) has been studied using potentiometric techniques under physiological conditions of temperature 37 C and ionic strength 0.15 moldm-3 NaCl and at different metal ion concentrations. Changes in pH were monitored with a glass electrode calibrated daily in hydrogen ions concentrations. The titration data within the pH range of 2.5-9.99 were analyzed to determine stability constants of hydroxide species using the SUPERQUAD program. Several different species were considered during the calculation procedure and the following hydroxides have been characterized: Ga(OH)3, Ga(OH)4- Ga3(OH)112-, Ga4(OH)11+ and Ga6(OH)153+. Speciation calculations based on the determined constants were then used to simulate the species distribution.