In order to get further understanding of lead ions adsorption onto ilmenite surface, zeta potential analysis, adsorption density calculation, FT-IR and XPS analysis were employed. The results showed that the adsorption of lead ions onto ilmenite surface was a chemically dominating process. Lead species could interact with iron-hydroxyl complex compounds to form a Fe–O–Pb complex. The hydrophobic complex of Pb(OL)2 was also observed. Iron and adsorbed lead ions on ilmenite surface served as the main active-sites via chemisorption with oleate species. Introducing lead ions, as a surface modification means, can efficiently improve ilmenite flotability.