ZSM-5/SBA-16 (ZS) supports were prepared using the two-step hydrothermal crystallization method. The effect of the aging temperature on the structural properties of the series ZS supports was studied. The prepared samples were analyzed by X-ray diffraction, scanning electron microscopy, N-2 physisorption, Al-27 magic angle spinning nuclear magnetic resonance, H-2 temperature-programmed reduction, Raman, X-ray photoelectron spectroscopy, pyridine Fourier transform infrared spectroscopy, and high-resolution transmission electron microscopy. The hydrodesulfurization performances of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) were examined at T = 340 degrees C and P-H2 = 4 MPa. The NiMo/ZS-45 catalyst synthesized at the aging temperature of 45 degrees C exhibited the best catalytic activities of DBT and 4,6-DMDBT, which were attributed to its regular shape, well-organized pore structure, high sulfidation degree, and a compromise between the acidity and metal support interaction (MSI, Mo-O-Si). Moreover, the possible DBT and 4,6-DMDBT HDS reaction networks over NiMo/ZS-45 were proposed.