Low aromaticity and a large number of oxygen-bridged bonds among the aromatic structural units of lignin make it possible to obtain chemicals directly. A novel Co/C@N catalyst with high activity towards hydrogenolysis of lignin-derived aryl ethers was synthesized according to the pyrolysis process of a predesigned ZIF-67. According to the results of characterization by powder X-ray diffraction (XRD), N-2 adsorption-desorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), Co was reduced by the carbonized organic linker of ZIF-67, and N was doped into the carbon skeleton of the catalyst. The effects of holding time, temperature, and initial H-2 pressure on the catalytic performance of Co/C@N were evaluated in the selective hydrogenolysis of benzyl phenyl ether (BPE). BPE was completely converted and the selectivity of monomer reached to 98.2% under optimized reaction conditions. The C-alk-O bond in BPE was first dissociated to form toluene and phenol, and then phenol was rapidly hydrogenated to form cyclohexanol. Furthermore, the Co/C@N catalyst shows high activity for hydroprocessing and selective cleavage of other lignin-derived aryl ethers, including phenylethyl phenyl, diphenyl ether, dibenzyl ether, dinaphthalene ether, guaiacol, anisole and veratrole. (C) 2019 Elsevier Ltd. All rights reserved.