The flotation of diaspore and kaolinite by one of a series of tertiary amines (DRN, DEN, DPN and DBN) was investigated. The tertiary amines show better floating recovery for kaolinite compared to diaspore. The maximum recovery D-value is 45% over a pH range from 3 to 8. FT-IR spectra confirm the presence of hydroxyl groups on the surface of kaolinite and diaspore. Zeta potential measurements show that the mineral surfaces are negatively charged over a wide pH range. Ionization of hydroxyl groups mainly accounts for the surface charging mechanism. The adsorption of tertiary amines onto the mineral surface is due mainly to electrostatic effects and the difference in electrostatic effect between a collector and the two minerals can explain the flotation separation. Inductive electronic and steric effects from the substituent groups result in different collecting powers for the four tertiary amines.