Hierarchically macro-/mesoporous structured Al2O3 and TiO2-Al2O3 materials were used as supports to prepare novel Co-Mo-Ni hydrodesulfurization(HDS) catalysts. A commercial Co-Mo-Ni/Al2O3 catalyst without macroporous channels was taken as a reference. The catalysts were characterized by scanning electron microscope(SEM), transmission electron microscope(TEM), energy-dispersive spectrometry(EDS), N2 adsorption-desorption, X-ray diffraction(XRD), and temperature programmed reduction(TPR). The apparent activities of the hierarchi-cally porous catalysts for thiophene HDS were superior to those of the commercial catalyst, which was mainly as-cribed to the diffusion-enhanced effect of the hierarchically bimodal pore structure. The addition of titania to alu-mina in the support helped to weaken the interaction between the active phase and the support, and as a result, the novel Co-Mo-Ni/TiO2-Al2O3 catalyst with a low titania loading(28%, by mass) in the support exhibited high HDS activities, even without presulfiding treatment. However, the catalyst with a high titania loading(61%, by mass) showed much lower activities, which was mostly caused by its low surface area and pore volume as well as the non-uniform distribution of titania and alumina. The kinetic analysis further demonstrated the support effects on HDS activities of the catalysts. Hierarchically macro- / mesoporous structured Al2O3 and TiO2-Al2O3 materials were used as supports to prepare novel Co-Mo-Ni hydrodesulfurization (HDS) catalysts. A commercial Co-Mo-Ni / Al2O3 catalyst without macroporous channels was taken as a reference. Catalysts were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), energy-dispersive spectrometry (EDS), N2 adsorption-desorption, X-ray diffraction (XRD), and temperature programmed reduction of the hierarchi-cally porous catalysts for thiophene HDS were superior to those of the commercial catalyst, which was mainly as-cribed to the diffusion-enhanced effect of the hierarchically bimodal pore structure. The addition of titania to alu-mina in the support helped to weaken the interaction between the active phase and the support, and as a result, the novel Co-Mo-Ni / TiO2-Al2O3 catalyst with a low titania loading (28% by mass) even without presulfiding treatment. However, the catalyst with a high titania loading (61% by mass) showed much lower activities, which was mostly caused by its low surface area and pore volume as well as the non-uniform distribution of titania and alumina The kinetic analysis further demonstrated the support effects on HDS activities of the catalysts.