Here we reported an experimental analysis of Al2O3-TiO2 binary mixed oxides used as supports of NiW hydrodesulfurization catalysts. The series of supports were prepared by soft template sol-gel synthesis assisted by four different surfactants (P-123(P), F-68(F), L-64(L) and CTAB(C)). The characterization results showed substantial differences in the formation of the mixed oxide, the surface, and the electronic. Noteworthy was the sharp unimodal pore-size distribution obtained in all cases. The surface composition measured by XPS confirmed surface enrichment with alumina, changing the activity of the NiW catalysts. The morphology of the active NiWS phase presented average slab length and stacking of about 2.3 nm and 2 slabs. Meanwhile, large quantities of curved slabs were observed. This fact confirmed that the WSx cluster interacts preferentially with the Al atoms instead with the Ti atoms. The highest activity was observed in the NiW/AlTi-P and NiW/AlTi-F sulfided catalysts. We noticed that the activity is related not only with the sulfidation degree, the Ni promotion, or the slabs length and staking but also with the slab shape and the interaction with the support. The results of this work confirm that these AlTi-x samples are suitable to be used as supports of hydrodesulfurization catalysts.