Bioavailable concentrations of polycyclic aromatic hydrocarbons (PAHs) were investigated in water of Three Gorges Reservoir (TGR) using semipermeable membrane devices during the period of completely impounding water. ∑PAH concentrations in water of TGR in the period of completely impounding water were 15-381 ng L(-1). ∑PAH concentrations increased from town or counties to big industrialized cities in TGR, indicating urbanization effects on PAH pollution in the water. Tributaries in TGR have a certain contribution of PAH pollution to the mainstream of Yangtze River and their pollution could not be neglected. An obvious decrease of PAH concentration was observed after 175-m water impounding in 2011 in TGR. Several factors may account for this decrease, including execution of comprehensive treatment and management measures in TGR, less rainfall in 2011, and sedimentation effect caused by the dam. Passive sampling method has been successfully applied in the investigation of trace PAH in water of TGR and proved to be a useful and efficient tool for the management and sustainable development of the big reservoir. The results of the study provide valuable information about PAH pollution in the whole reservoir including some tributaries, and the pollution status is dynamically related with human activities. Therefore, PAH could be used as a marker compound or indicator in the network monitoring system to surveil and trace the pollution status in TGR.