A micro-scale investigation was carried out by applying an atomic force microscope (AFM) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy to study in situ the adsorption of three different collectors — oleic acid, octanohydroxamic acid (HA) and salicylhydroxamic acid (SHA) — on bastnaesite in aqueous solutions. The results show that all three collectors adsorb on bastnaesite. The hydroxamic acid collectors — HA and SHA — adsorb on bastnaesite mainly in the form of insoluble metal hydroxamate. Their specific adsorption mechanism indicates that high selectivity will be achieved with a hydroxamic acid collector for the flotation of bastnaesite.