The concentration and speciation of six heavy metals in sediments of eight sampling sites of Haihe River were investigated. The metals, namely Cd, Cu, Co, Ni, Mn and Pb were considered. By using sequential extraction (SE), the total metals were divided into five fractions: exchangeable, carbonate bound, iron/manganese oxide bound, sulfides and organic matter fraction and residual fraction. A multivariate statistical approach (principal component analysis, PCA) was used to evaluate the contamination of heavy metals by the total levels and chemical forms, respectively. The results showed that the total metals concentration (TMC) could not provide sufficient and accurate information because the mobility, bioavailability and toxicity of metals depend not only on their total concentration but also on the physicochemical form in which they occur.