Reverse flotation of collophanite at natural pH could significantly decrease the cost of pH regulators. In this study, isooctyl polyoxyethylene ether phosphate (AEP) was tested as a new surfactant in the reverse flotation of collophanite. Micro-flotation tests were conducted, and the adsorption mechanism of the new collector was analysed using X-ray photoelectron spectroscopy (XPS) and zeta potential analyses. The results of the flotation tests demonstrated that AEP could enable dolomite to float under natural pH (pH=7.2) and showed profound selectivity towards dolomite as opposed to fluorapatite. Based on the zeta potential and XPS results, the adsorption phenomena are mainly attributed to calcium active sites on both mineral surfaces. Dolomite possesses more magnesium active sites than fluorapatite, which tend to reinforce the interaction effect between AEP and dolomite. Furthermore, when compared to CO32- ions on the dolomite surface, PO43- ions on the fluorapatite surface tend to exhibit a stronger hindrance to the adsorption of AEP on the fluorapatite surface. This is attributed to their larger volumes and more charges on their surfaces, thereby causing a floatability difference between the two minerals.