<p>The development of highly active and stable non-precious catalysts for selective hydrogenation of phenol to cyclohexanol is significant but challenging. Here, CeO₂ nanorod supported Ni nanoparticles with oxygen vacancy structural defects were constructed via direct pyrolysis of metal organic framework (MOFs) for catalytic hydrogenation of phenol. Results showed pyrolysis temperature and time had an obvious effect on the catalytic performance. Under the reaction conditions of 160 °C, 2&#xa0;MPa, 2&#xa0;h, Ni@C/CeO₂-1&#xa0;h − 400 °C catalyst prepared at temperature of 400 °C and time of 1&#xa0;h exhibited the best catalytic performance with 94.7% phenol conversion and 100% cyclohexanol selectivity due to the highly dispersed Ni nanoparticles. Further increase in pyrolysis temperature or extension of pyrolysis time both resulted in the decrease of the catalytic performance. In addition, results also found the Ni@C/CeO₂-1&#xa0;h − 400 °C catalyst with a rod-like structure displayed higher phenol conversion than purchase CeO₂ supported Ni (Ni@C/CeO₂-pur) catalyst. The enhanced catalytic performance of Ni@C/CeO₂-1&#xa0;h − 400 °C catalyst is ascribed to the higher concentration of oxygen vacancies. This work provides the design and synthesis of highly efficient non-noble catalysts for the production of value-add chemicals from biomass.</p>