The Xiangjiang River (XR), located in Hunan province in south-central China, is the second largest tributary of the Yangtze River. The occurrence, and sources of the polycyclic aromatic hydrocarbons (PAHs) in the 20 surface sediment samples from XR were analyzed, and the biological risks of the PAHs on the benthic organisms were assessed using sediment quality guidelines. The results showed that the occurrence level of the 16 USEPA priority PAHs in the surface sediments ranged from 190 to 983 ng/g (dry weight) with a mean concentration of 452 ± 215 ng/g. The concentration of phenanthrene was the highest with a mean concentration of 104 ± 44 ng/g. The compositions and principal components analysis indicated that the PAHs in the sediments in XR were mainly from pyrogenic sources which could be attributed to the open burning of rice straws and coal combustion of the local industries in the XR basin. The PAH contamination in the sediments was considered to be moderate, and has posed a small adverse biological effect on the benthic organisms.