Iron oxides are abundant in natural waters and soils and have high capacities for scavenging Pb(II) by adsorption, which affects the transport and fate of Pb on the earth's surface. We investigated the adsorption of Pb (II) on magnetites substituted with commonly incorporated transition metals such as Cr, Mn, Co, and Ni. The adsorption capacity, mechanism, and local coordination of Pb(II) were investigated by traditional macroscopic studies, i.e., acid-base titration and batch adsorption experiment, complemented with X-ray absorption fine structure (XAFS) spectrum analysis and surface complexation model (SCM). The substitution increased the surface site density, while pHpzc did not vary. Pb(II) adsorption was not suppressed by the presence of background electrolyte and improved as pH increased. The isotherms were well fit to the Langmuir adsorption model. The XAFS analysis demonstrated that Pb(II) ions were adsorbed on magnetite surface predominantly via innersphere complexation, where the adsorbed Pb(II) species was in bidentate binuclear corner-sharing geometry, independent of the adsorption capacity. This adsorption geometry can be applied to fit the experimental adsorption data well with the diffuse layer model (DLM). The substitutions improved the adsorption capacity in the following order: Cr > Ni > Mn > Co, and were discussed regarding the measured values of active site density and local coordination of adsorbed Pb(II). This study is the first documentation of Pb(II) adsorption on magnetite with different substitutions. The obtained results are of great significance for the understanding of Pb(II) surface complexation reactions on magnetite surface.