The distribution characteristics and correlation analysis of Fe speciation in the surface sediments from different reaches along Yellow River have been analyzed utilizing the so-called sequential extraction approach. The results indicate that the concentration of total iron (∑Fe) in the surface sediments is in the range from 14.01g/kg to 30.98 g/kg, Liulin (H13) sample is the maximum and Bohai offshore (H21) sample is the minimum. The residue iron(Fe-6)-the highest concentration in all speciations with 92.55%~98.4% of ∑Fe, and the bio-available fraction iron (BFe) only for 1.56%~6.98% with remarkably positive correlation with ∑Fe, the change trades of BFe, Fe-6 and ∑Fe concentrations are consistency along main stream of the Yellow River. The organic matter (OM) shows a notable correlation with both BFe and Fe-Mn oxides (Fe-4), while BFe has extremely positive correlation with Fe-4, indicating that the content of BFe mainly relies on the Fe-4 and the organic matter. When the concentration of total particulate matter (TPM) is increased in the water of the Yellow River, such as in the middle reaches of the Yellow River Dayudu segments (H15) and Sanmenxia segments (H17), one can find the high concentration of ∑Fe and Fe-1 in the surface sediments, when the concentration of TPM decrease, such as in the upper reaches of the Yellow River Wuhai segments (H7) and Sanshenggong segments (H8) , the concentration of ∑Fe and Fe-1 in the surface sediments is low. The results indicate that the artificial dams in the Yellow River Basin cause the changes of TPM concentration in the water, and also lead to non negligible impact on the iron cycle in the Yellow River.