The selective conversion of phenolic materials is a well-adopted solution to upgrade lignin-based bioresources into high-value bio-oil in biomass refinery industries. This study focused on four main aspects: characterization, selection of catalysts, reaction dynamics behaviors, and mathematical modelling. A model lignin, that is, phenol, was selectively transformed into cyclohexanol by using the prepared Ni–xCo/γ-Al2O3 catalysts in a subcritical water medium. The hydrogenation results showed that when using 15 wt% of Ni–3Co/γ-Al2O3 particles, both total mole yield and selectivity of cyclohexanol could reach approximately 80%, which further indicated that the particles are suitable for catalytic hydrogenation of phenol in subcritical water. Moreover, a reaction kinetics model was developed by chemical reaction kinetics and least squares regression analysis, the robustness and predictability of which were also verified.