Catalytic hydrodeoxygenation (HDO) is a promising route to upgrade bio-oils from plants or pyrolysis to basic chemicals. KA-oil (cyclohexanol/-one) is an example of a highly valuable feedstock for the industrial synthesis of caprolactam and perlon, which can potentially be produced via a completely sustainable route. This work investigates the alkaline promoter effects on Ni-based catalysts for the selective HDO of lignin surrogate guaiacol using mesoporous Ni/MgO and co-impregnated Ni-MgO/SiO₂ catalysts. Due to preferred demethoxylation by alkaline oxides and their accumulation on nickel corners, responsible for dehydration, conversion, and selectivity for KA-oil rise. Furthermore, influences of operating parameters are investigated and optimized by design of experiments (DoE), while long-term stability (24 h) and water resistance remain high. In a final proof of concept, the application of Ni-CaO/SiO₂ was the most promising material (U=93 %, S=86 %), demonstrating a sustainable route from lignin-based bio-oil to produce a bulk commodity for caprolactam synthesis.