Adsorption mechanisms of Pb on soil with high CaCO3 content were investigated by combined batch sorption and X-ray absorption fine structure (XAFS). Date from the batch equilibrium studies showed that Pb sorption was nonlinear and was well fitted to Langmiur isotherm. The XAFS data indicated that Pb could be adsorbed via the inner-sphere complex, the precipitation of calcium carbonate containing Pb (PbCaCO3), and outer-sphere Pb sorption complex. The formations of inner-sphere complexes and PbCaCO3 implied strong metal interactions with the surfaces the mechanistic reason for the affinity of Pb for CaCO3 as observed in macroscopic studies. At low metal concentration, 500 mg·L-1 of initial Pb, radial distance of the first-shell Pb—O (R1) was 0.169 2 nm, however, at 1 000 mg·L-1 of initial Pb, the R1 was 0.166 8 nm. These revealed that the percentage of inner-sphere complexes increased when the initial Pb was increased from 500 to 1 000 mg·L-1.