Rare earth element (REE) production is limited in part by inefficient strategies for beneficiation. Hydroxamic acid ligands are promising reagents for the selective flotation of bastnäsite [(Ce,La)FCO3], a major REE ore mineral, but the mechanism and energetics of adsorption are not understood, interfering with the design of new, more efficient reagents. Here, the adsorption of octyl hydroxamic acid onto bastnäsite was measured using a combination of experimental and computational methods. In-situ atten- uated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy revealed changes in the hydroxamate functional group vibrational frequencies, corresponding to chelation with cerium cations at the bastnäsite surface. The results indicate a monodentate chemisorption mechanism at low surface loading that changes to bidentate chemisorption at higher concentrations. This interpretation is sup- ported by molecular vibrational frequency shifts calculated using density functional theory (DFT), and orientation of the hydrocarbon chain measured by sum frequency generation (SFG) vibrational spec- troscopy. The binding enthalpies of octyl hydroxamic acid interacting with La and Ce-bastnäsite surfaces were measured using isothermal titration calorimetry (ITC) revealing a stronger coordinating ability with bastnäsite than with a common gangue mineral, calcite (CaCO3). Because octyl hydroxamate favors mon- odentate adsorption at low surface coverages, the relative chelating strength of metal ions could be a poor predictor for selectivity under monolayer adsorption conditions. At higher surface loadings, where the bidentate mode of adsorption is active, selectivity is likely to be limited by increased flotation of gangue ores.