Ordered mesoporous alumina (OMA), and commercial non ordered mesoporous alumina (CMA) were used as support to synthesize NiMo catalysts with a metal loading of 16%Wt. OMA synthesis was made using Pluronic (P123) as structure directing agent, and ethanol as a solvent. The physical and chemical properties of the supports and catalysts were characterized by XRD, nitrogen physisorption, X-ray photoelectron spectroscopy (XPS), Transmission electron microscopy (TEM), acidity of support was studied by n-butylamine adsorption followed by FTIR and catalytic performance was evaluated by hydrodesulphurization of dibenzothiophene (DBT) reaction. Main difference of supports is a two-dimensional arrangement of pores on OMA support and a threedimensional arrangement for CMA. OMA support has more surface area available to disperse Mo and Ni species than the CMA material, besides OMA present slight acidity on its surface, and these characteristics of support leaded to obtain a NiMoS2 active phase better structured to present higher activity for DBT hydrodesulphurization and higher selectivity for direct desulfurization than the obtained for CMA supported catalyst, despite CMA presented interconnected pores and higher pore diameter.