A nano-scale investigation has been carried out by applying an AFM (atomic force microscope) to study in situ the adsorption of various collectors, i.e., oleic acid, octanohydroxamic acid (HA), and salicylhydroxamic acid (SHA), on bastnaesite in aqueous solutions. The obtained AFM images show that the surface morphology of bastnaesite changes greatly after it contacts the solutions of the collectors, suggesting that all these collectors can effectively adsorb on bastnaesite. Increasing temperature can help increase the adsorption of oleic acid on bastnaesite. FTIR (Fourier transform infrared) results also show that all these collectors adsorb strongly on bastnaesite with a strong absorbance spectra being detected, which confirms with the results obtained with AFM imaging analysis. In general, hydroxamic acid collector (HA and SHA) adsorbs on bastnaesite mainly in the form of insoluble metal hydroxamate. This specific adsorption mechanism explains that a high selectivity with a moderate collectivity will be achieved with a hydroxamic acid collector for the flotation of bastnaesite.