4-nitrophenol (4-NP), a toxic pollutant, is ubiquitous in the environment and difficult to degrade in natural conditions. To deal with this contaminant, catalytic reduction of 4-NP is a promising way. Herein, we report a copper and cobalt nanoparticle decorated carbon framework (Cu/Co@CF) through a self-sacrificial template method derived from the copper cobalt carbonate hydroxides/zeolitic imidazolate framework-67 (CuCoCH/ZIF-67) composite. Served as a cobalt and copper source as well as a self-sacrificial template, CuCoCH extended the pore sizes of carbonized derivatives of ZIF-67 and synchronously transformed to bimetallic active sites. The catalyst exhibited a highly efficient catalytic performance and remarkable reusability for hydrogenation of 4-NP. The 4-NP conversion reached 99.7% in 1 min and the pseudo-first-order reaction kinetic constant was 5.122 min-1, which is the highest among similarly reported catalysts.