Abstract: A novel composite material (TD) composed of TS-1 microcrystalline and dendritic mesoporous silica nanospheres (DMSNs) was successfully prepared. The TD composite material had open pore structure and large specific surface area, which was conducive to the mass transfer of reactants and products. The Ti element in TS-1 could be used as an electron assistant, and the spillover d-electrons were conducive to the improvement of the sulfidation and dispersion of MoS2, thereby forming more type II MoS2 active phases. The incorporation of Ti could bring more Brønsted (B) and Lewis (L) acid, which was conducive to the hydrogenation pathway (HYD) selectivity (41.2%) of dibenzothiophene (DBT) hydrodesulfurization (HDS) and isomerization (ISO) route selectivity (21.9%) of 4,6-dimethyldibenzothiophene (4,6-DMDBT) HDS, thus improve the HDS activity of DBT and 4,6-DMDBT. NiMo/TD-70 (Aging temperature = 70 °C) had the best HDS activities of DBT (99.0%) and 4,6-DMDBT (93.7%) due to its large open pore structure, good acidity, suitable metal-support interaction (MSI) and perfect dispersion of the metallic active sites.