The selective production of hydrocarbons for the chemical industry from biogenic feedstock is a significant challenge when ensuring hydrocarbon and fuel supply, despite the heterogeneity of this feed. In this study, guaiacol, as a surrogate for complex lignin-based biomass resources, is converted by an inert silica carrier material with different d-metal impregnation (Mo, W, Re, Fe, Co, Ni, Cu, Pd, Ag) to reveal the reasons for different product selectivity to hydrogenated and deoxygenated hydrocarbon products. Hydrogen at 15 bar (gauge) and guaiacol are converted on metal/silica catalysts between 250 °C and 400 °C, while the physicochemical catalyst properties are characterized before and after catalytic tests. Volcano plots for the conversion, hydrogenation and deoxygenation products versus the d-band energy, surface atom distance and fouling properties reveal three groups of metals: (i) those that are less active and show high coking (Ag, α-Fe); (ii) those that show high activity for hydrogenation (β-Co, Ni, Pd) and, therefore, preferably yielded cyclohexane, cyclohexanol and 2-methoxycyclohexanol; (iii) those that preferably promote deoxygenation (Mo, W, Re, Cu) and, therefore, promoted the formation of phenol, benzene, anisole and catechol. The results are summarized in a pseudo van Krevelen diagram and interpreted as a complex interdependency from Sabatier’s principle of geometric correspondence of hexagonal metal surface for hydrogenation, electronic correspondence for the activation of hydrogen and electronic correspondence by oxophilicity for deoxygenation from the d-band center model.