Cyclohexanone is an important intermediate for the synthesis of nylon, but the direct hydrogenation reaction of phenol to cyclohexanone can easily generate cyclohexanol. In this paper, the in situ synthesis strategy is used to grow the layered double hydrotalcites on alumina. Compared with the pristine alumina, the modified support has increased specific surface area, average pore size and abundant acid-base sites on the surface. Pd/MgAl-LDO@Al₂O₃ catalyst was then prepared by the calcination of precursor with layered structure, followed by the impregnation of Pd. The catalyst is used for the selective hydrogenation of phenol (reaction conditions: phenol/Pd=1000 mol/mol, 80 ℃, 0.4 MPa H₂). The obtained Pd/MgAl-LDO@Al₂O₃ shows enhanced catalytic performance under a high substrate/Pd ratio. Detailly, when the phenol conversion is 97%, the cyclohexanone selectivity can reach 88%. High-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analysis are performed to characterize the catalyst, and it is found that in situ growth of hydrotalcite-like structure on alumina can effectively decrease the average particle size of Pd and then increase the dispersion of active component. Moreover, when Ni is introduced into the layered structure, PdNi alloy structure could be obtained by the easy reduction process of using NaBH₄. Kinetics study indicates the energy barrier of the phenol hydrogenation reaction over Pd/NiAl-LDO@Al₂O₃ is lower than that over Pd/MgAl-LDO@Al₂O₃ due to the formation of PdNi alloy. But the alloy structure leads to an obvious decrease of cyclohexanone selectivity. According to the product distribution and characterization results, a possible mechanism is proposed. Phenol is adsorbed on the surface of the basic sites on the Pd/MgAl-LDO@Al₂O₃ catalyst in a non-coplanar manner, which is conducive to the selective hydrogenation of phenol to produce cyclohexanone and inhibits the over-hydrogenation of cyclohexanone. After repeated use for 5 times, the Pd/MgAl-LDO@Al₂O₃ catalyst shows excellent stability. The phenol conversion could keep at ca. 90% and the cyclohexanone selectivity maintains ca. 90%.