Fluoride mainly exists in minerals such as phosphate rock and fluorite, which are associated with calcite gangue minerals. Under the condition of the flotation separation of the weak acid, mineral surface of F- will be partically dissolved and adsorbed to the mineral surface, thus affecting the mineral surface properties. The adsorption behavior of F- on calcite surface and the effect of F- on calcite surface properties were studied in this paper. The results show that F- is adsorbed on calcite surface by chemisorption at 5.5 pH value of calcite pulp, and the adsorption amount increases gradually with the increase of time, and F- adsorption by calcite reaches equilibrium at 90 min. When sodium oleate (NaOL) is used as collector, the presence of F- weakens the hydrophobicity of calcite surface. Zeta potential test, solution chemistry calculation and X-ray photoelectron spectroscopy (XPS) analysis show that the F- reacts with Ca2+on calcite surface to form CaF2 precipitation, which occupies Ca sites on calcite surface and reduces the adsorption of NaOL on calcite surface.