As an important strategic resource, tungsten ore is a superior resource in China. Flotation technology has been the main technology for the separation of complex tungsten resources. The feasibility and efficiency of flotation separation depend on the mineralogy characteristics of ore, which is closely related to the geological mineralization. From the perspective of geochemistry, the principle of tungsten mineralization and its relationship with flotation are summarized in this paper. In the mineralization of tungsten, granite magmatic differentiation, high F content, and surrounding rock properties are very crucial to the enrichment and mineralization of tungsten, and determine the migration and mineralization of tungsten and deposit types. Different tectonic–magmatic mechanisms contribute to the different deposit types and there are great differences in the types and contents of gangue minerals in these different deposits. Accordingly, a series of tungsten ore flotation technologies were developed, such as fatty-acid flotation of the quartz vein type, fatty acid roughing-heating cleaning of the greisen type, and chelating collector roughing—heating cleaning of the skarn type. Especially for complex high-calcium scheelite and wolframite mixed ore, the flotation technology of complex collector greatly improves the efficient exploitation and utilization of tungsten resources. The geological ore-forming principles of tungsten ore not only determine the essential characteristics of the ore, but also provide a new train of thought for the development of tungsten utilization.