Kyanite and sillimanite are two polymorphic minerals with the same formula of Al 2 SiO 5 , but different crystal structures. Despite their high economic values, selectively recovering them by flotation is a challenge. In this study, the flotation behaviors of the two minerals with sodium oleate as the collector were examined at different pH conditions. Zeta potential measurement, infrared spectroscopic measurement, chemical speciation and X-ray photoelectron spectroscopy measurement were conducted to identify the underpinning mechanisms. It is found that the flotation behavior of both minerals is different under the same flotation condition. The flotation recovery of sillimanite is much higher than that of kyanite in the presence of the collector sodium oleate. Sodium oleate adsorbs onto the surfaces of kyanite and sillimanite mainly through the chemical interaction of the ionic-molecular dimers with aluminum atoms at pH 8.0. The higher sillimanite flotation recovery between the two minerals is related to the higher electrostatic charge densities of the aluminum atoms in six-fold coordination, which leads to the higher collector adsorption.