The AlKIT-5 sample with Fm3m symmetry order structure and different Si/Al ratios was first synthesized by chemical grafting method. The Al-27 NMR result of the AlKIT-5 sample proves that most aluminum species have been incorporated into the silicon framework. The oxidized supports and catalysts were characterized by XRD, N-2 adsorption, Al-27 MAS NMR, SEM, TEM, Py-FTIR, and Raman spectroscopy, and the series of sulfided catalysts were investigated by XPS and HRTEM. The corresponding NiMo catalysts were obtained by impregnation method, and the hydrodesulfurization activity for dibenzothiophene (DBT) was tested in a high-pressure microreactor under different weight hourly space velocity (WHSV, 10-100 h(-1)) values. All of the catalysts based on KIT-5 mesoporous material support showed better HDS efficiencies than that of the NiMo/AIMCM-41 catalyst, benefiting from the interconnected large pore structure. The NiMo/AK-10 catalyst exhibited the best HDS activity (99.2%) when the WHSV was 10 h(-1), which resulted from the moderate acidity and good dispersion of Ni and Mo active species.