Fluorite, a key strategic mineral, is indispensable in high-tech industries such as aerospace, semiconductors, and environmental protection. Global fluorite reserves, led by China, Mexico, and South Africa, underscore its strategic value, especially as high-tech demands rise. This chapter focuses on the development and utilization of fluorite resources associated with tungsten tailings, which are often overlooked due to their complex mineralogy and challenging separation processes. The various flotation reagents, including anionic collectors like fatty acids and sulfonic acids, cationic collectors, amphoteric collectors, and combined collectors were reviewed, which have shown promise in improving the selectivity and recovery of fluorite. The use of inhibitors such as water glass, sodium hexametaphosphate, and organic inhibitors like tannic acid and starch is also discussed, emphasizing their role in achieving effective separation of fluorite from gangue minerals. The chapter further explores the challenges in the development and utilization of associated fluorite resources, particularly the need for new technologies to address the comprehensive recovery of complex and low-grade ores. The case studies of Shizhuyuan Polymetallic Mine in Hunan Province and Huangshaping Tungsten-Molybdenum Polymetallic Mine in Hunan demonstrate the successful application of these technologies, resulting in significant improvements in fluorite recoveries and economic benefits. The efficient development and utilization of fluorite resources from tungsten tailings are vital for ensuring the sustainable supply of fluorine chemicals, which are essential for the growth of strategic emerging industries.