Comparative studies of flotation of oleate on diaspore and kaolinite in different particle size fractions (0.075–0.038 mm, 0.038–0.01 mm, 0–0.01 mm) are presented to investigate the influences of particle size. The flotation results show that the kaolinite recovery increases with a decrease in particle size, while the case of diaspore is the opposite. Chemisorptions of anionic oleate collector on the surface Al sites of the negatively charged diaspore and kaolinite are confirmed by zeta potential and FTIR measurements. Anisotropic surface broken bond densities are calculated based on surface crystal chemistry to characterize anisotropic wettability of mineral crystals. The increasing order of broken bond densities (Db) and hydrophobicity for different crystal planes of diaspore and kaolinite correlate well with increasing the number of broken AlO bonds. The anisotropic adsorption of oleate on different crystal planes of diaspore and kaolinite are studied in terms of interaction energies computed by molecular dynamics (MD) simulations. The oleate is adsorbed more readily on (0 1 0) than (0 0 1) for diaspore. As for kaolinite, the oleate adsorption is considerably less on (0 0 1) as compared to (1 10 ). The conclusions drawn from purely theoretical computations are in good agreement with our experimental contact angle results.