The modification of catalytic activity through the use of metallic promoters is a key strategy for optimizing performance, as electronic factors play a crucial role in regulating catalytic behavior. This study explores the electronic factors behind the adsorption of glycerol (Gly) on bimetallic nickel-based compounds (${\mathrm{Ni}}_3\mathrm{X}$) using density functional theory (DFT) calculations; incorporating Mn, Fe, Co, Cu, and Zn as promoters effectively tunes the d-band center of these systems, directly influencing their magnetic, adsorption, and catalytic properties. A good correlation between the calculated glycerol adsorption energy and the d-band filling of the studied bimetallic surfaces was identified. Interestingly, this correlation can be rationalized using the celebrated Newns–Anderson model based on the calculated d-band fillings and centers of the systems under study. Additionally, the adsorption energies and relative stability of other electro-oxidation intermediates toward dihydroxyacetone (DHA) were calculated. Notably, the ${\mathrm{Ni}}_3\mathrm{Co}$ and ${\mathrm{Ni}}_3\mathrm{Cu}$ systems exhibit an optimal balance between glycerol adsorption and DHA desorption, making them promising candidates for glycerol electro-oxidation. These theoretical insights address fundamental aspects of developing glycerol valorization processes and advancing alcohol electro-oxidation technologies in fuel cells with noble-metal-free catalysts.