The structural and acidic properties of sol-gel prepared alumina powders as catalyst supports were modified by adjusting the hydrolysis ratio, R (i.e. molar ratio of water relative to the alumina precursor, R = [H2O]/[aluminium-tri-sec-butoxide(ASB)]). Structural properties (e.g. porosity) and acidic properties were measured for alumina powders prepared with various R values, from 3 to 13. For R < 9 and R > 10, first-order particles were closely packed with ink-bottle-type pore structures, whereas for R = 9 or 10, first-order particles were loosely packed with a spatial fractal arrangement that yielded pseudo-cylindrical pore structures. In addition, the alumina powders prepared with R = 9 or 10 had larger water pore volume and stronger acidity than those with other R values. These properties unique to the powders prepared with R = 9 or 10 were ascribed to relatively short Al-O-Al chain lengths that resulted in loose packing of first-order particles. The results here indicate that alumina powders with favorable properties as catalyst supports (e.g. mean pore diameter) can be tailored by selecting the appropriate R in the sol-gel synthesis process.