AbstractPhenol amination to various valuable amines has attracted considerable attention in heterogeneous catalysis, but limited studies have focused on non‐noble metal catalysts. This study reports a bifunctional catalyst (Ni/SiO2‐AE) containing nickel nanoparticles and Lewis acid sites derived from nickel phyllosilicates for efficient amination of phenol to cyclohexylamine. The Ni/SiO2‐AE catalyst resulted in 89.4% phenol conversion and 86.0% selectivity to cyclohexylamine at 160 °C for 2 h, which outperforms the catalysts by conventional deposition‐precipitation (Ni/SiO2‐DP) and wetness‐impregnation (Ni/SiO2‐WI). The turnover frequencies based on the actual exposed metal surface area for Ni/SiO2‐AE, Ni/SiO2‐DP, and Ni/SiO2‐WI are calculated as 71.7, 49.0, and 8.7 h−1, respectively. Results demonstrate that the Ni nanoparticles exsoluted from nickel phyllosilicates participate in the activation of dihydrogen molecules, and the Lewis acid sites stemmed from coordination unsaturated Ni2+ sites on the catalyst serve to adsorb and activate phenol. The synergistic effect of the dual‐functions intensifies the phenol amination.