As a result of thermodynamic analysis of fluorite–sodium oleate–water system, flotation and adsorption tests at various pH values and sodium oleate concentrations, it has been established that regularities of fluorite flotation cannot be explained by the oleate of alkali-earth metals formation on its surface. The hypothesis, connecting optimal conditions for mineral flotation with zero charge of its surface, allowed to explain the regularity of mineral flotation observed and elaborate a quantitative physicochemical model of fluorite flotation suitable for improving industrial processes and application of automatic control systems at the plants.