Using dual mesoporous titania as a support, due to the presence of intrinsic Brönsted acid sites, the main approach to 4,6-dimethylbenzothiophene (46DMDBT) hydrodesulfurization (HDS) becomes the direct desulfurization (DDS) route through isomerization and dismutation reactions, instead of the hydrogenation (HYD) pathway usually observed with a conventional promoted (by Ni or Co) MoS2/Al2O3 catalyst.