Using GC-MS 18 PAHs have been quantified in sediments from water source areas, tributaries and sewage outfalls at the reaches of Huaihe River (Huainan to Bengbu). The results show that the concentrations of total PAHs ranged from 308.12-1090.37 ng/g in sediments from water source areas and tributaries, and 1308.36-8793.16 ng/g in sediments from sewage outfalls. 3-4 rings were the dominant compounds compared to the 5-6 ring PAHs. Black carbon showed better correlation to PAHs than that of TOC. The composition characterization, principal component analysis and particular ratios of PAHs demonstrated that incomplete combustion of fossil fuels was the main source of PAHs in sediments at reaches of Huaihe River (Huainan to Bengbu), as well as a few anthropogenic releases of oil products. Ecological risk assessment indicated that, most of PAHs compounds in sediments have exceeded ER-L and ISQV-L values, among which part PAHs compounds at Yaojiawan even exceeded ER-H and ISQV-H values, showing the significant potential risk of PAHs to the ecosystem in the study area.