A kind of Ni-MoS3 material with a prismlike hollow structure was prepared through three steps: the preparation of a nickel precursor, the preparation of a NiMoS4 hollow structure intermediate product, and the annealing treatment of NiMoS4. Then, the catalytic activity of this material in slurry-phase hydrogenation of heavy oil was evaluated. Characterization results indicated that under suitable preparation conditions, the prepared hollow material with a Mo content of 23.40 wt % and a Ni content of 7.08 wt % had a length of approximately 340 nm, a width of approximately 300 nm, and a shell wall thickness of approximately 10 to 20 nm. Moreover, in addition to Ni, Mo, and S, the surface of the material also contained O and C, and the Mo4+ on the surface of this hollow material accounted for 77.24 wt % of the surface Mo atoms, which indicated that more Mo4+ with higher hydrogenation activity may be stably present on the surface of this hollow material than Mo in other valence states. In the slurry-phase hydrogenation reaction of fluid catalytic cracking slurry, this prepared Ni-MoS3 hollow material showed higher catalytic activity than the compound catalyst of molybdenum naphthenate and nickel naphthenate with similar metal composition, indicating that the hollow material can more effectively utilize the metal to create more active sites, thereby providing higher hydrogenation activity and coke inhibition.