SiC and B-doped SiC were prepared and employed to support Ni components for the catalytic hydrogenation of nitroarenes. The B-doping of SiC evidently improved the catalytic activity of Ni/SiC, and the activity of Ni/SiC-B0.5 catalyst was 2.4 times higher than that of undoped Ni/SiC. Further investigations revealed that the incorporation of B substituted some Si atoms in SiC lattice and thus produced carbon vacancies. These vacancies will result in a heterogeneous distribution of surface charges on SiC, thereby enhancing the adsorption and activation of nitroarenes on the support surface. In addition, the carbon vacancies can also act as donor centers for capturing dissociated hydrogen species, thus enhancing the hydrogen spillover from Ni to SiC surface.