The effect of titanium as a promoter for the nickel-cobalt/silica-titania (NiCo/Si-Ti) catalyst in the hydrogenation of phenol was comparatively studied. In the phenol hydrogenation under mild reaction conditions (1 MPa H2 pressure and 100 °C), the Ti-promoter induces the formation of the Coδ−−OV−Ti3+ active sites and enhances the hydrogenation activity of the NiCo/Si catalyst to convert phenol to cyclohexanol. The catalytic hydrogenation with the optimal composition of the NiCo/Si-1.0Ti (Si:Ti ratio of 8.5:1) catalyst was completed within 1 h (conversion 98.2 % and selectivity >99 %), which was more efficiently than that with other Ti-doped catalysts and NiCo/Si as baseline, indicating a strong positive synergistic effect between the metal (Ni-Co) and support (Ti-Si) components of the catalyst in this reaction. Additionally, the kinetics, pathway and catalytic mechanism of the hydrogenation of phenol are also examined. Furthermore, the NiCo/Si-1.0Ti catalysts also showed a good performance at reducing the unstable oxygenated compounds in the bio-oil.