Scheelite and wolframite, the national strategic mineral, are usually enriched by froth flotation basing on the different physical and chemical properties among tungsten ore and other gangue minerals. Based on the crystal structures of scheelite and wolframite, their anisotropic physical and chemical properties such as surface broken bond, cleavage and exposed surface, surface energy, wettability, surface electrokinetic and adsorption properties were studied and summarized. The relationships between different surface properties, and the separation mechanism of scheelite were explained. Surface broken bond density (Db) was positively correlated with surface energy. A crystal surface with lower Db and surface energy will be easily exposed when the comminution of the minerals. For wolframite, the main exposed surfaces are {111} and {100}, while {112}, {101} and {001} for scheelite. The adsorption strength of sodium oleate on crystal surfaces of a mineral is primarily influenced by the number of broken bonds present on the unit crystal surface. The anisotropy of surface electrical properties and adsorption could be explained by the differences in the active oxygen, calcium sites and their broken bonds. The exposure of highly active crystal surfaces and shape parameters of scheelite particles can be tuned by optimizing the grinding process, and hence enhancing its flotation.