Using FTIR (DRIFTS and IRRAS) and XPS spectroscopy, xi potential measurements, and Hallimond flotation tests, we confirmed that long-chain primary amines are adsorbed on silicates at pH 6-7 through the 2D-3D precipitation mechanism. The orientation and packing of dodecyl- and hexadecylammonium acetate and chloride adsorbed on albite in the different regions of the adsorption isotherm were determined: It was shown that these characteristics depend strongly on the substrate. Coadsorption of the counterion was not revealed, but the counterion was found to affect indirectly the adsorption at concentrations above the, concentration of the bulk amine precipitation.