Flotation separation of magnesite and its calcium-containing carbonate minerals is a difficult problem. Recently, new regulators have been proposed for magnesite flotation decalcification, although traditional regulators such as tannin, water glass, sodium carbonate, and sodium hexametaphosphate are more widely used in industry. However, they are rarely used as the main regulators in research because they perform poorly in magnesite and dolomite single-mineral flotation tests. Inspired by the limonite presedimentation method and the addition of a regulator to magnesite slurry mixing, we used a tannin pretreatment method for separating magnesite and dolomite. Microflotation experiments confirmed that the tannin pretreatment method selectively and largely reduces the flotation recovery rate of dolomite without affecting the flotation recovery rate of magnesite. Moreover, the contact angles of the tannin-pretreated magnesite and dolomite increased and decreased, respectively, in the presence of NaOl. Zeta potential and Fourier transform infrared analyses showed that the tannin pretreatment method efficiently hinders NaOl adsorption on the dolomite surface but does not affect NaOl adsorption on the magnesite surface. X-ray photoelectron spectroscopy and density functional theory calculations confirmed that tannin interacts more strongly with dolomite than with magnesite.