Zeolite catalysts have shown significant advantages in hydrogenation reactions due to their ordered pore structure and abundant acid sites. Common zeolites exhibit pore accessibility limited to microporous states, which restricts their application in diffusion-limited processes. In this study, a steam-seeding-assisted colloidal crystal template (SSAC) method was used to prepare ZSM-5 zeolite with a three-dimensionally ordered macroporous (3DOM) structure, which was then loaded with nickel phosphide for hydrodenitrogenation reactions. SEM and TEM characterization demonstrated that the prepared zeolite material possessed a highly ordered 3DOM structure with interconnected macropores. XRD, FT-IR, and BET analysis indicated that the macroporous zeolite material exhibited a typical MFI structure, mesoporous channels, and a higher specific surface area. The high external surface area facilitated the formation of uniformly sized Ni2P nanoparticles on the zeolite surface. The introduction of macroporous structures also leads to suitable Brönsted acid and Lewis acid sites in zeolite materials. The resultant Ni2P/3DOMZSM-5 catalyst exhibited higher reaction rate constants and TOF (10.87×10−2 μmolg−1s−1 and 1.5×10−3s−1, respectively) compared to other zeolite catalysts and commercial catalysts.