Mesostructured titania as support for the CoMoS active phase in deep hydrodesulfurization (HDS) of 4,6-dimethydibenzothiophene (4,6-DMDBT) leads to an increase of the intrinsic HDS activity and a higher selectivity for direct desulfurization (DDS) for HDS reaction in contrast with the conventional CoMoS/alumina catalyst. The temperature treatment of the mesostructured TiO2 support, modifies the catalyst's activity for the transformation of 4,6-DMDBT. The higher total and HDS activities were obtained after treatment at 380 degrees C corresponding to the higher specific surface area and to a mesostructured TiO2 material with a semi-crystalline anatase framework. Beyond 550 degrees C, the specific surface area decreases strongly corresponding to a complete crystallization of the mesopores walls into anatase structure. Moreover, the temperature under which the support is treated prior its impregnation has no impact on the selectivity of the transformation routes of the sulfur compound.