Abstract: The combined use of fatty acid collectors and chelating collectors is an important research direction for wolframite flotation. The single mineral test method was used to study the effect of the combination of GYB chelating collector and three representative fatty acid collectors of 731, GYR and TAB-3 on the flotation behavior of wolframite and gangue minerals.Furthermore, the mechanism of combined use of GYB, TAB-3 and the two collectors were discussed by Zeta potential measurement, Infrared spectroscopy methods. The results showed that the combined use of GYB and fatty acid collectors increased the maximum recovery of wolframite flotation to above 70%, and reduced the total dosage of collectors by about 1/2; among the three fatty acid collectors, TAB-3 reagent had the strongest collecting ability to wolframite, which recovery of wolframite was 78%, and the weakest collecting ability to fluorite, quartz, calcite gangue minerals; the combination of GYB and TAB-3 made the surface potential of wolframite move negatively, and the absorption peaks of the infrared spectrum on its surface shift to a high wave number, such as the C=N stretching vibration absorption peak of GYB and the C-H stretching vibration peak of TAB-3. Then the adsorption capacity of the two collectors on the wolframite surface was stronger than the collector was used alone, and the adsorption form was chemical adsorption.