Separating rare-earth-element-rich minerals from unwanted gangue in mined ores relies on selective binding of collector molecules at the interface to facilitate froth flotation. Salicylhydroxamic acid (SHA) exhibits enhanced selectivity for bastnäsite over calcite in microflotation experiments. Through a multifaceted approach, leveraging density functional theory calculations, and advanced spectroscopic methods, we provide molecular-level mechanistic insight to this selectivity. The hydroxamic acid moiety introduces strong interactions at metal-atom surface sites and hinders subsurface-cation stabilization at vacancy-defect sites, in calcite especially. Resulting from hydrogen-bond-induced interactions, SHA lies flat on the bastnäsite surface and shows a tendency for multilayer formation at high coverages. In this conformation, SHA complexation with bastnäsite metal ions is stabilized, leading to advanced flotation performance. In contrast, SHA lies perpendicular to the calcite surface due to a difference in cationic spacing. We anticipate that these insights will motivate rational design and selection of future collector molecules for enhanced ore beneficiation.