The distribution, source, ecological risk and ecotoxicity of polycyclic aromatic hydrocarbons (PAHs) of sediments from 7 sampling sites, named as Xinyang (XY), Huainan (HN), Bengbu (BB), Xuyi (XuY), Fuyang (FY), Mengcheng (MC) and Zhengzhou (ZZ), in the Huaihe River basin, China, have been investigated. The total concentrations of 16 USEPA priority PAHs ranged from 62.9 to 2232.4 ng g⁻¹ dry weight (d.w.) with a mean concentration of 1056.8 ng g⁻¹ d.w. Through the assessment of ecological risk, we found that the levels of PAHs in the Huaihe River should not exert adverse biological effects. The total benzo[a]pyrene toxicity equivalent (TEQ) values calculated for samples varied from 0.01 to 194.1 ng g⁻¹ d.w., with an average of 65.9 ng g⁻¹. The toxicity data were accordant with the chemical analysis results in this study. HN, BB and ZZ showed the greatest pollution extent both in the chemical analysis and the study of ecotoxicological effects.