Aluminated mesoporous silica was prepared by multiple post-grafting of alumina onto uniform mesoporous SiO₂, which was assembled from monodisperse SiO₂ microspheres. Hydrodesulfurization (HDS) catalyst was prepared by loading Ni and Mo active components onto the aluminated uniform mesoporous SiO₂, and its HDS catalytic performance was evaluated using hydrodesulfurization of dibenzothiophene as the probe reaction at 300 ℃ and 6.0 MPa in a tubular reactor. The samples were characterized by N₂ physisorption, scanning electronic microscopy, Fourier transform infrared spectrum, X-ray diffraction (XRD), temperature-programmed desorption of ammonia (NH₃-TPD), ²⁷Al nuclear magnetic resonance (²⁷Al-NMR) and high-resolution transmission electron microscopy (HRTEM). The results showed that the Si–OH group content of SiO₂ was mainly dependent on the pretreatment conditions and had significant influence on the activity of the NiMo catalyst. The surface properties of the aluminated SiO₂ varied with the Al₂O₃-grafting cycles. Generally after four cycles of grafting, the aluminated SiO₂ behaved like amorphous alumina. In addition, plotting of activity of NiMo catalysts supported on aluminated meso– macroporous silica materials against the Al₂O₃-grafting cycle yields a volcano curve.