In this work, two collectors sodium oleate (NaOL) and benzohydroxamic acid (BHA) were used to study the synergic effect in wolframite flotation. The flotation behaviour of these collectors was investigated at various NaOL:BHA ratios. Results show that the mixtures of NaOL with BHA of different ratios result in large improvements in the recovery of wolframite and the 9:1 NaOL:BHA ratio of collector mixture produced the highest wolframite recovery. The amount of NaOL and BHA adsorbed on wolframite was measured for these various reagent mixtures. Compared with pure NaOL, the addition of a certain proportion of BHA is beneficial for NaOL adsorption. Molecular dynamics simulations indicate the formation of HOL–HA (oleic acid–benzohydroxamic acid) complex can take place spontaneously in NaOL–BHA system. Additionally, HOL–HA complex interact with the huebnerite (MnWO4) surface more easily than NaOL–HOL (the highest surface active composition in sodium oleate) and the addition of BHA enable the H of carboxyl group in HOL to generate hydrogen bonds with O atoms of huebnerite surface, resulting in a stronger affinity of mixed surfactants. These results reveal that in a binary NaOL–BHA system, the BHA can encourage greater adsorption of the NaOL.