The Yangtze River Delta (YRD) is one of the most populated and economically prosperous regions in China and contains numerous chemical industry parks. To understand the distribution and sources of polycyclic aromatic hydrocarbons (PAHs), surface water and sediment samples were collected from areas around the industrial parks. The total concentrations of 19 PAHs in water and sediment were 32.98–286 ng L−1 and 15.14–5355 ng g−1, respectively. The highest PAH concentrations in water and sediment were found in samples from Wuxi city, which were dominated by high molecular weight (HMW) PAHs, and strongly influenced by fine chemical parks. HMW compounds dominated in the sediment with PAHs containing four and five rings accounting for 61% of the sedimentary ΣPAHs, PAHs in water were dominated by low molecular weight (LMW) compounds (PAHs with two and three rings represented >68% of ΣPAHs). The results of isomeric ratio analysis and principal component analysis with multiple linear regression indicated that the PAH concentrations in water and sediment near the YRD chemical parks are strongly influenced by industrial emissions. The fugacity fraction approach was applied to explain the trend for water–sediment exchange of 16 priority PAHs, which showed that net fluxes for most were from the sediment into water. The results indicated that the LMW PAHs were in a non-steady state in the sediment–water system. An ecological risk assessment showed that most sites were low to medium risk, but one site was high risk.