To improve the floatability of tungsten minerals, lead ions (lead nitrate) were used to modify the surface properties of the minerals and benzohydroxamic acid (BHA) was used as a collector in the flotation system. Pb2+-BHA complexes are inevitably present in this process and the role of it is unclear. This investigation is going to describe a new approach and the mechanism of catalyzing BHA adsorption onto scheelite by lead ions. Chemical speciation, zeta potential, FTIR, and XPS studies were conducted to establish the important role of lead ions. Indeed, Pb2+-BHA complexes were shown to be the active species responsible for flotation. The speciation and zeta potential results showed the presence of the adsorbed Pb2+-BHA complexes on the scheelite. The XPS results for atomic composition and binding energies confirmed Pb2+-BHA species adsorbed on the scheelite surface, which contributed to more adsorption of BHA. The new method would increase the recovery of scheelite, simplify the flowsheet and reduce the processing cost.