Several studies revealed that flotation of wolframite changes with different Fe/Mn ratios, but they did not reach a consensus. This relationship in the presence of benzohydroxamic acid (BHA) and sodium oleate (NaOl) as collectors was studied in this paper through comparison of probability distribution curve of wolframite with different Fe/Mn ratios between the raw ore and the flotation concentrate, the pure mineral flotation and solution chemistry of flotation. The results showed that wolframite with high Fe/Mn ratio showed higher flotation with BHA as a collector while the flotation behavior of wolframite was completely opposite with NaOl as a collector. Besides, the calculations of chemical equilibrium in the solution were plotted as ΔG°-pH graphs. The results revealed that the flotation of wolframite may be determined by the interaction between BHA and ferric(II) ion or between NaOl and manganous ion. From the perspective of collector mixture, the results also explain the high collecting capability of the BHA/NaOl collector mixture, which can be defined as “functional complementation”.