Abstract: Tungsten is an important strategic metal，which is of great significance to the national defense security，national resources security andthe development of strategic emerging industries.The development of tungsten flotation chemistry has solved a series of key bottleneck problems of complex tungsten flotation and provides the important supports forthe efficient and clean development and utilization of the complex scheelite and the scheelite and wolframite associated resources in China.The advance of tungsten mineral flotation reagents and technologies were reviewed. And the relationship among mineralogy，crystal chemistry，solution chemistry，and flotation was developed. During the geological mineralization，fluorite and calcite are usually associate with tungsten minerals，leading to the difficulties the flotation separation of calcium minerals.The subtle difference in crystal structure and interfacial properties provide the feasibility for the flotation separation. Modified fatty acid，cationic collector，chelate collector，metal complex collector，and the assembly of surfactants realized the flotation separation between tungsten minerals and calcium minerals. A simplified flotation process using Pb-BHA complexes was developed to replace the energy-inefficient Petrov's process of using a fatty acid，increasing the recovery of scheelite and reducing the cost. In summary，the geological mineralization mechanism，crystal chemistry and solution chemistry oftungsten ore determine the difficulty of tungsten ore flotation separation and guide the development of tungsten ore flotation reagents and new technology，which provides a solid support for cleaner development of complex tungsten resources.

Key words: tungsten ore, flotation chemistry, geological mineralization mechanism, crystal chemistry, flotation reagents, flotation technology