As a commercial adsorbent, TiO2 shows a high adsorption capacity for lead (Pb(II)). However, the molecular structure of Pb(II) adsorption on TiO2 is still unknown. Meanwhile, as a widely used corrosion inhibitor, phosphate (PO4) is usually added into drinking water, and its influential mechanism on Pb(II) removal by TiO2 remains unknown. Here, the mechanisms of Pb(II) adsorption on TiO2 and the effect of PO4 were systematically investigated using a combination of spectroscopic analyses and surface complexation modeling. The adsorption structure of Pb(II) on TiO2 was revealed as a tridentate mononuclear configuration by the extended X-ray absorption fine structure (EXAFS) analysis. In the presence of 0.1-5 mg/L PO4, Pb(II) was removed mainly by adsorption on TiO2 rather than precipitation. Ternary complexation between Pb(II) and PO4 on TiO2 surfaces was found based on EXAFS and in situ Fourier transform infrared characterizations. These complexation structures were used to build a surface complexation model to accurately simulate and predict Pb(II) removal under different conditions. This study provides essential information about the mechanisms of Pb(II) removal by TiO2 and develops a model to predict adsorption behaviors, especially in the presence of PO4.