The studies for microfine mineral flotation have focused on the two main directions of increasing the apparent mineral particle size and reducing the bubble size, while little research has been reported on the special surface properties and adsorption mechanisms of mineral particles of different sizes. In this study, sodium oleate was chosen as a typical surfactant. The mechanism of the effect of smithsonite particle size on the heterogeneity and adsorption behavior of the mineral surface was explored in depth. Through microflotation experiments, BET area tests, Washburn contact angle tests, particle agglomeration tests, adsorption tests and inorganic carbon analysis, it was pointed out that the smaller the size of the particles, the greater the surface wettability, and the smaller the density and thickness of adsorbed oleate on the surface. The difficulty of encapsulating the mineral surface with a hydrophobic layer of oleate hydrocarbon chains, as well as suboptimal particle aggregation sizes, are key reasons for the poor flotation behavior of fine smithsonite. Furthermore, the inhomogeneity of active sites and charge distribution of surface components of smithsonite with different sizes was revealed from a microscopic point of view by DRIFT spectroscopic analysis, XPS analysis and zeta potential measurements. As the particle size of smithsonite decreases, the positive charge density on the surface is higher and the hydration tendency is more intense, hindering the adsorption of oleate. This work is expected to guide the full particle size recovery of minerals in the flotation from a novel microscopic point of view.