Abstract: A method for the determination of 16 polycyclic aromatic hydrocarbons(PAHs) in groundwater samples by high performance liquid chromatograph (HPLC) with fluorescence and ultraviolet detectors was established. The determination condition for HPLC was optimized and applied for practical water sample analysis. Under optimized condition, the detection limits of the method for PAHs were 0.001~0.01 μg/L and the recoveries were 86.3%~105% with precision of 0.39%~2.55% RSD (n=7). The method provides the advantages of simple operation, accuracy, high efficiency and is suitable for the determination of trace PAHs in groundwater samples.