Vibrational spectroscopy and X-ray photoelectron spectroscopy (XPS) studies have been carried out to investigate the interaction of n-octanohydroxamic acid, acetohydroxamic acid and potassium hydrogen n-octanohydroxamate with a copper electrode, malachite and cuprite. Bulk analysis, XPS, Raman and FT-IR have been used to characterise the reactants, surface products and the bulk copper compounds. Copper aceto- and n-octanohydroxamates have been shown to have a 1:1 stoichiometry. XPS results for cuprite and malachite minerals show the formation of a layer of copper n-octanohydroxamate under the conditions investigated. Surface enhanced Raman scattering (SERS) studies at gold coated malachite mineral surfaces have been attempted with acetohydroxamic acid, the acid potassium salt of n-octanohydroxamic acid and the commercial collector AM28.