Hollow porous carbon (HPC) composed of inner voids and outer shells, is receiving increasing attention in constructing supported catalysts for diverse applications. It is of great allure but still challenging to controllably tune the secondary porous structure (pore in the outer shells) of the HPC support to improve the performance of the catalysts. Herein, a Ni-substituted ZIF-67 was used as a precursor to prepare HPC-supported catalysts. We found that Ni2+ can partially substitute Co2+ to create "defected structure" within ZIF-67, and the secondary pore structure of the derived HPC can be facilely tuned by adjusting the ratio of Ni2+ to Co2+. Catalyst HPC-Ni-ZIF-1 with hierarchical secondary pore and the largest pore volume exhibits an excellent catalytic performance for the hydrogenation of nitro compounds to corresponding amino compounds.