Liaohe River Basin is an important region in northeast China, which consists of several main rivers including Liao River, Taizi river, Daliao River, and Hun River. As a highly industrialized region, the basin receives dense waste discharges, causing severe environmental problems. In this study, the spatial and temporal distribution of aqueous polycyclic aromatic hydrocarbons (PAHs) in Liaohe River Basin from 50 sampling sites in both dry (May) and level (October) periods in 2012 was investigated. Sixteen USEPA priority PAHs were quantified by gas chromatography/mass selective detector. The total PAH concentration ranged from 111.8 to 2,931.6 ng/L in the dry period and from 94.8 to 2766.0 ng/L in the level period, respectively. As for the spatial distribution, the mean concentration of PAHs followed the order of Taizi River > Daliao River > Hun River > Liao River, showing higher concentrations close to large cities with dense industries. The composition and possible sources of PAHs in the water samples were also determined. The fractions of low molecular weight PAHs ranged from 58.2 to 93.3 %, indicating the influence of low or moderate temperature combustion process. Diagnostic ratios, principal component analysis, and hierarchical cluster analysis were used to study the possible source categories in the study area, and consistent results were obtained from different techniques, that PAHs in water samples mainly originated from complex sources, i.e., both pyrogenic and petrogenic sources. The benzo[a]pyrene equivalents (EBaP) characterizing the ecological risk of PAHs to the aquatic environment suggested that PAHs in Liaohe River Basin had already caused environmental health risks.