Selective hydrogenation of phenol is a green strategy to produce cyclohexanone. Achieving high phenol conversion and cyclohexanone selectivity under mild conditions is a significant challenge in the design and synthesis of highly efficient catalysts. Herein, a highly efficient Pd@CN-rGO catalyst is synthesized by supporting Pd nanoparticles on the composite of ZIF-derived N-doped carbon and reduced GO (CN-rGO), which is prepared via annealing the composite of layered ZIF-L-Co and GO. The as-fabricated Pd1.2@CN-rGO-15 catalyst shows superior catalytic performance in phenol hydrogenation, and its turnover frequency (TOF) is 33.7 h(-1), 3.2 times higher than that of Pd1.6/rGO and 1.5 times higher than that of Pd0.9@CN-rGO-0. The synergistic effect of CN and rGO leads to the uniform dispersion of Pd, high phenol adsorption ability, and strong antioxidizability of Pd, which contributes to the superior catalytic performance. More importantly, Pd@CN-rGO has good reusability in phenol hydrogenation. These findings will offer new insights into the development of high-performance catalysts for the selective hydrogenation of phenol.