Metal confinement catalyst MoS2/Pt@TD-6%Ti (TD, TS-1/Dendritic mesoporous silica nanoparticles composite) in dendritic hierarchical pore structures was synthesized and showed excellent sulfur-resistance performance and stabilities in catalytic hydrodesulfurization reactions of probe sulfide molecules. The MoS2/Pt@TD-6%Ti catalyst combines the concepts of Pt-confinement effect and hydrogen spillover of Pt noble metal. The modified micropores of Mo/Pt@TD-6%Ti only allow the migration and dissociation of small H2 molecules (0.289 nm), and effectively keep the sulfur-containing compounds (e.g. H2S, 0.362 nm) outside. Thus, the MoS2/Pt@TD-6%Ti catalyst exhibits higher DBT and 4,6-DMDBT HDS activities because of the synergistic effect of the strong H2 dissociation ability of Pt and desulfurization ability of MoS2 with a lower catalyst cost. This new concept combining H2 dissociation performance of noble metal catalyst with the desulfurization ability of transition metal sulfide MoS2 can protect the noble metal catalyst avoiding deactivation and poison, and finally guarantee the higher activities for DBT and 4,6-DMDBT HDS.