A green method for the synthesis of 4-methoxycyclohexanone was established in this paper. Catalytic hydrogenation of 4-methoxyphenol was first carried out over supported nickel-based catalysts. Subsequently, the hydrogenation solution was oxidized by hydrogen peroxide to further improve the selectivity for the target product. The influence of two kinds of preparation methods, including deposition-precipitation and impregnation method, as well as reaction conditions on the activity and stability of the catalysts for hydrogenation was investigated. As demonstrated by X-ray diffraction (XRD), H2-temperature programmed reduction (H2-TPR) and Transmission electron microscopy (TEM) characterizations, the Ni/Al2O3-DP catalyst, prepared by a deposition-precipitation method, exhibited higher dispersion, smaller particle, and stronger interaction between the active particles and the support, compared with the Ni/Al2O3-IMP catalyst, prepared by an impregnation method. These structural characters account for its superior catalytic activity and stability in 4-methoxyphenol hydrogenation. In the hydrogenation of 4-methoxyphenol, Ni/Al2O3-DP was used as catalyst. The optimum reaction conditions were as follows: reaction temperature 423 K, reaction pressure 4.0 MPa, reaction time 1 h, m(4-methoxyphenol): m(Ni/Al2O3-DP) = 6:1.The effect of the oxidation conditions was also investigated to achieve better results. It was found that the total selectivity for 4-methoxycyclohexanone can reach 95.3%, while the reaction temperature is 353 K, the reaction time is 20 h, and the ratio of n(4-methoxycyclohexanol): n(sodium tungstate): n(oxalic acid) : n(hydrogen peroxide) is 100: 1: 1: 250.