In this paper. surface physiochemical properties of three typical aluminas, gamma-Al(OH)(3), gamma-Al2O3, and alpha-Al2O3, were investigated by means of XRD, SEM, TEM, BET surface area, TG/DTA, and potentiometric titration techniques. Based on the titration data, surface protonation and deprotonation constants were determined using the constant capacitance model (CCM). The emphasis of this research was laid on the comparison of the crystal structure, surface hydration/dehydration and acid-base properties of these three typical alumina minerals. The calculation results revealed that the surface acidity of the aluminas is in the order of alpha-Al2O3 > gamma-Al(OH)(3) > gamma-Al2O3 after being hydrated for 1 h. The correlation between the hydration/dehydration mechanisms of alumina and its acid/base properties is discussed. (c) 2006 Elsevier Inc. All rights reserved.