The reduction of the size and modification the surface of Ni-0 are generally used to improve the hydrogenation performances of Ni-based catalysts. In this work, a new method derived Ni-0@carbon nanostructure was constructed on SiO2 in order to explore an alternative way to improve the intrinsic activity of Ni-0 in the selective hydrogenation of p-chloronitrobenzene (p-CNB). The experimental and computational results exhibit that the synergistic effect between Ni-0 core and nitrogen-doped carbon shell (Ni-0@C-N) can dissociate more hydrogen on larger Ni-0 core (similar to 14 nm) than Ni-0@C (Ni-0 = 11 nm), while the external surface of carbon shell facilitates the oblique adsorption of p-CNB and the consequent hydrogenation. Such formed dual-reaction surfaces inhibit the dechlorination reaction but increase the active hydrogen species. Consequently, Ni-0@C-N/SiO2 catalyst (similar to 14 nm) adversely displays similar to 2.3-fold higher turnover frequency and similar to 100% p-chloroaniline selectivity, in contrast to Ni-0@C/SiO2 (similar to 11 nm) and the commercial Raney Ni (similar to 6 nm) catalysts.