AbstractThe linear relations between adsorption energies are one of the cornerstones of contemporary catalysis in view of the simplicity and predictive power of the computational models built upon them. Despite their extensive use, the exact nature of scaling relations is not yet fully understood, and a comprehensive theory of scaling relations is yet to be elaborated. So far, it is known that scalability is dictated by the degree of resemblance of the adsorbed species. In this work, density functional theory calculations show that CO and OH, two dissimilar species, scale or not depending on the surface facet where they adsorb at Pt alloys. This peculiar behavior arises from an interplay of ligand and geometric effects that can be used to modulate adsorption‐energy scalability. This study opens new possibilities in catalysis, as it shows that surface coordination is a versatile tool to either balance or unbalance the similarities among adsorbates at alloy surfaces.