Abstract: Calcite and wollastonite are often associated with each other in ore. For the same Ca²⁺ contained in the mineral lattices, some similar surface characteristics and dissolution characteristics are shown in the two minerals. But for the existence of the different anionic groups in their mineral lattices, some differences are shown in the flotations of the two minerals. In this paper, the floatability differences of calcite and wollastonite were studied by the single mineral test when lauryl amine and sodium oleate were used as collectors. The surface potentials and the chief components of calcite and wollastonite in solutions under different pH values were studied by zeta potential analysis and logC-pH analysis of the two minerals. The density of calcium exposure and the density of unsaturated bonds of calcium on the surfaces of calcite and wollastonite were studied by XPS analysis and MS simulations. The results of zeta potential and logC-pH analysis showed that the surface potentials of calcite were more than wollastonite due to the different locating ions of the two minerals; XPS and MS simulation results showed that calcite had more density of calcium exposure and the density of unsaturated bonds of calcium than wollastonite.