Abstract: Three-dimensionally interconnected macroporous (3DM) Al₂O₃ was prepared by phase separation. Macropore size of the obtained Al₂O₃ is 250 nm with a bimodal pore distribution (at about 21 and 250 nm, respectively) and the BET specific surface area of 174 m²/g, as well as the crushing strength of 16.5 N/mm. Ni and Mo on the 3DM catalyst are uniformly dispersed on the surface of the support. The active phases of sulfurized catalyst possess length of 3−10 nm and stacking layers of 1−7. The stacking distribution of active phase more than 4 layers is about 40%, forming a non-uniform active phase structure. Compared with the industrial catalysts, the hydrodemetallization (HDM) rate, hydrodesulfurization (HDS) rate and hydrodecarbonization (HDCCR) rate of the 3DM catalyst increase by 6.2%, 6.0% and 6.8%, respectively. The pore structure, surface properties, active phase structure and their synergistic effect may be the main reasons for the excellent catalytic performance of the 3DM catalyst.