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Collector OA, oleic acid, is widely used industrially for fluorite flotation. Low selectivity, dispersibility and collecting capability of the OA collector are always observed. In this study, compared with flotation of dolomite, a collector mixture of OA and SPE (styrylphenol polyoxyethylene ether) demonstrated significantly better performances for the fluorite. An optimal mass ratio 4 : 1 OA : SPE was found, and the recovery of fluorite was increased from over 85 % to more than 94 % compared with pure OA. Furthermore, the dosage of the collector agent was reduced from 50 mg mL−1 to 20 mg mL−1, which did not negatively impact the recovery of dolomite. The results from the contact angle tests indicated that SPE selectively increased the surface hydrophobicity of fluorite but had little effect on dolomite. Besides, zeta potential measurements and IR analyses revealed that the addition of SPE led to strong chemical adsorption on the surface of fluorite, resulting in a significant difference in the flotation performances of the two minerals. Therefore, SPE‐emulsified OA is corroborated to prompt more selectivity and collecting capability on flotation of fluorite over dolomite., Styrylphenol polyoxyethylene ether (SPE) was used as an emulsifier in the separation of fluorite and dolomite and the mechanism was studied. Micro‐flotation results showed that SPE could improve the recovery of fluorite at a reduce collector dosage. Contact angle measurements demonstrated that SPE increased the hydrophobicity of fluorite. Therefore, the shortcomings of poor OA selectivity in the separation flotation of fluorite and dolomite can be effectively improved by using SPE as an emulsifier.