The iron oxide such as goethtie and humic substances (HS) are the important active components for metal ions binding in the natural soils. In the previous study for the modeling the Pb binding in the goethtie/HS/Pb ternary system, the Linear additivity (LA) model always underestimeted the Pb bound by the solid phase. This caused by the fact that the positively charged goethtie can interact with the negatively charged HS strongly and this interction was not inclued in the LA model. In this study, the effect of soil fulvic (JGFA) and humic acid (JGHA) on Pb binding to goethite was studied with the Ligand Charge Distribution (LCD) model and X-ray Absorption Fine Structure (XAFS) analysis. In the LCD modeling, the inner-sphere complex between the –FeOH^-0.5 of goethite and –COOH of HS and three main types of Pb bound as Pb-goethite (Pb bound to goethite), Pb-HS-goethite (Pb bound to adsorbed HS) and goethite-Pb-HS (Pb bound as bridge between goethite and HS) were considered. The spatial distribution of the small JGFA particles was equal in Stern layer. However part of the large JGHA particles was presented in diffuse layer which was determined by the JGHA diameter and environmental conditions. the results showed that Pb binding to goethite-HS complexes could be described reasonably well with the LCD model and the speciation distribution of Pb was analyzed. At low Pb levels, Pb-bridges were important for both JGFA and JGHA. At high Pb levels and low HS loading, Pb-goethite almost dominates over the entire pH range; but at high HS loading, the primary species was goethite-HS-Pb at acidic pH and goethite-Pb at alkaline pH. Compared with JGFA, there was a constant contribution of Pb-bridge about 10% for the JGHA. For the Linear Combination Fit (LCF) analysis of EXAFS spectra for the ternary systems, the spectra of the binary systems goethite-Pb and HS-Pb were applied as the reference. The fitting results indicated that with the increased HS loading more Pb was bound to the adsorbed HS and less to goethite, which supported the present LCD calculations. The present knowledae contibutes to a deeper insight into the role of FA and HA in affecting the amount and speciation of metal ions in soil systems, which is very useful for improving the accutacy of the risk assessment for heavy metal ion pollution in soils and the evaluation of environmental quality.