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To enhance the performance of traditional cationic collector, a novel polyhydroxy amine collector N-(2,3-Propanediol)-N-dodecylamine (PDDA) was designed by introducing one propylene glycol group into dodecylamine (DDA). It was prepared by a nucleophilic substitution reaction, which showed better solubility and hydrophobicity than DDA and was firstly employed as the collector for the separation of hematite and quartz. Flotation tests showed that PDDA had an excellent flotation performance and significantly better selectivity than DDA. In addition, the flotation performance and adsorption mechanism of PDDA on hematite and quartz surfaces were studied using Fourier transform infrared spectroscopy (FT-IR), zeta potential and X-ray photoelectron spectroscopy (XPS) tests. These results demonstrated that the interaction between PDDA and the minerals’ surfaces was mainly electrostatic adsorption and hydrogen bond, while PDDA tended to adsorb on the surfaces of quartz more than that of hematite. Performance optimization of amine collectors by introducing hydroxyl was also verified, which was of great meaning to the design, development, and application of the polyhydroxy cationic collector. In conclusion, PDDA could be used as a potential collector in the flotation separation of quartz and hematite.