A series of gamma-A1(2)O(3) materials with different textural properties and acidities were synthesized from the boehmite sol by tuning the aging temperatures. NiMo supported catalysts were prepared by using gamma-Al2O3 as the supports, then the catalytic HDS performance were evaluated by using DBT and 4,6-DMDBT to be the probe molecules. The physico-chemical properties of gamma-Al2O3 supports and the corresponding NiMo catalysts were characterized by XRD, N-2-physisorption, Py-IR, UV-Vis DRS, laser Raman spectra, H-2-TPR, XPS, HRTEM methods. The characterization results showed that NiMo/gamma-363 catalyst possessed a large pore size (12.0 nm), open pore volume (0.86 cm(3) g(-1)), moderate acidity and appropriate MSI. The NiMo/gamma-363 catalyst presented the highest DBT and 4,6-DMDBT conversions at all the WHSVs. The NiMo/gamma-363 catalyst showed highest k(HDS) and TOF values of the 4,6-DMDBT HDS, which could be ascribed to the synergistic effect of excellent textural properties, appropriate acidity and suitable MSI of the NiMo/gamma-363 catalyst, moderate dispersion degree, high sulfidation degree and desirable stacking morphology of the MoS2 crystallites. The highest HYD/DDS ratio (1.51) of the 4,6-DMDBT HDS over the NiMo/gamma-363 catalyst indicated that the HYD pathway was the main reaction route. Furthermore, a possible reaction network for 4,6-DMDBT HDS over the series of NiMo/gamma-Al2O3 catalysts was proposed. (C) 2017 Elsevier B.V. All rights reserved.