Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy have been undertaken to determine the nature of the interaction of n-octanohydroxamate with bastnaesite and rare earth oxides. Hydroxamate compounds of the rare earths, neodymium, erbium, dysprosium, gadolinium and holmium have been synthesised, and characterised by vibrational spectroscopy. Nd hydroxamate was also investigated by photoelectron spectroscopy, and its stoichiometry confirmed as Nd(hydroxamate)3 by gravimetric analysis. Neodymium oxide, bastnaesite (cerium) crystals (Pakistan) and Mountain Pass ore samples were treated with hydroxamate. Interaction was observed at the surface of both the rare earth oxides and the minerals. The research reported has established the feasibility of applying vibrational and photoelectron spectroscopy to study the interaction of hydroxamate collectors with rare earth minerals.