With the continuous exploitation of wolframite resources, the raw ore gradually tends to be poor and fine. Flotation has become an effective means to improve the recovery efficiency of fine wolframite. In recent years, study of flotation technology has mainly focused on the development of flotation reagents. Taking the development of wolframite flotation reagents as the starting point, the development of collectors, activators and inhibitors in wolframite flotation was introduced. The combination methods, advantages and disadvantages and indexes of reagents were described in detail. The flotation process mechanism of flotation reagents and the mechanism of solid-drug surface action were analyzed. The results show that the chelating collector has strong selectivity, but the cost of the reagent is high, the manufacturing process is complex and the stability is poor, and there are few reagents that can be applied in actual production. Fatty acid collectors are widely used because of their strong collecting ability and low price, but their selectivity will be reduced, and they are often used in combination with other agents. The collecting performance of arsonic acid and phosphonic acid collectors is better than that of fatty acid collectors, but because of its high price and environmental pollution, it has not been applied in actual industrial production. The combined use of collectors can not only reduce the production cost of mines, but also reduce the use of toxic agents to a certain extent. Highly selective activators and inhibitors can achieve efficient separation of wolframite slime and gangue minerals. According to the existing situation, new reagents with high selectivity, low dosage, environmental protection and non-toxicity should be developed according to different ore properties.