In this study the effects and mechanism of lead ions influence on wolframite flotation with benzohydroxamic acid (BHA) were studied through micro-flotation, adsorption experiments, zeta potential measurements, logarithmic concentration diagram, and X-ray photoelectron spectroscopy. It was observed that lead ions could significantly enhance the recovery of wolframite in flotation and adsorption density of collector BHA onto the wolframite surface. The results showed that Pb existed in the forms of lead ion, monohydric lead, and lead hydroxide at the water-wolframite interface respectively, at three pH ranges. They increased the zeta potential of wolframite. However, the zeta potential of wolframite was still negative, resulting in repulsive electrostatic force to anionic collector BHA. Combining with XPS spectra, it revealed the chemisorption of BHA onto the wolframite surface. In addition, PbO or Pb(OH)2 was observed on the wolframite surface due to the reaction between lead ions and wolframite. These reaction products increased the adsorption site of BHA on the wolframite surface because Pb-hydroxamate was found on the wolframite surface.