A series of 0.6TiO(2). 0.4Al(2)O(3) catalytic supports has been prepared by both non-hydrolytic route and hydrolytic sol-gel processes. Some synthesis variables, such as the use of ethylene glycol as complexing agent, the generation in situ of the hydrolysis water, or the separated hydrolysis of the respective alkoxides, have been studied for the samples prepared by the hydrolytic sol-gel method. The physical and structural characterisation of the samples has been carried out by different techniques. The textural results show that the surface area and the pore size distribution are influenced by the synthesis method, which also affects the thermal behaviour and the crystallization process of the samples. The distribution of acid sites is also different, depending on the synthesis conditions.