Boron was introduced into nickel/acid-treated bentonite (Ni/A-Bn) catalysts to improve the anti-coking ability of the nickel-based catalyst in the hydrogenation of nitrobenzene. The results showed the B-doped Ni/A-Bn catalyst was more active than that without B. During an extended reaction period, Ni-B/acid-treated bentonite (Ni-B/A-Bn) resulted in a high nitrobenzene conversion and a high aniline selectivity. The lifetime of Ni-B/A-Bn was extended significantly compared with that of Ni/A-Bn. The addition of B into Ni/A-Bn decreased the NiO particle size, improved the dispersion of active components, and decreased carbon deposition. The combination of B and Ni prevented coke deposition on metallic Ni during nitrobenzene hydrogenation, which reduced carbon deposition on the surface of Ni-B/A-Bn.