Abstract A group of hydrodesulfurization (HDS) catalysts, based on transition metal sulfides (Co-Mo-W) and supported on mechanically-mixed mesoporous silicas (SBA-15 and SBA-16), have been synthesized and characterized by physicochemical methods (DRS-UV–vis, Micro Raman spectroscopy, XRD, SEM, HRTEM, EDS and catalytic activity). It has been demonstrated that the use of a mixture of silicas with two different porous structures has an advantage with respect to the use of the SBA-15 and SBA-16 separately for the preparation of supported catalysts for hydrodesulfurization reactions of refractory sulfur compounds, such as dibenzothiophene. This is because the presence of different porous structures has a positive effect over the diffusion processes of the precursors of the active phases on the support, and the whole result is a higher catalytic activity for the HDS reactions of dibenzothiophene, even more than that of the commercial catalyst used as a comparative model; this activity is also related with the stage of the synthesis process in which the mixture is done.