Abstract: Polycyclic aromatic hydrocarbons(PAHs) in water can cause cancer, teratogenesis and mutagenesis, which are harmful to ecosystems and human health. Therefore, the accurate and convenient determination of PAHs content in water is of great significance. In this study, the water samples were enriched by solid-phase extraction(SPE). After concentration by nitrogen blowing, the qualitative and quantitative analysis of samples was conducted by gas chromatography-tandem mass spectrometry(GC-MS/MS) in multiple reaction monitoring(MRM) mode. The experimental parameters were optimized, including different extraction methods, types of extraction columns, pH of extraction solution, types of matrix modifiers, residual chlorine content and removal methods, volume of extracted water samples, and chromatographic and mass spectrometric conditions. 0.1 g of ascorbic acid was added into 1 000 mL of water sample to remove the residual chlorine followed by adjusting pH ≤ 2 with phosphoric acid. Then 25 g of sodium chloride, 10 mL of isopropanol and 10 mL of n-hexane were added as the matrix modifiers. Finally, 16 kinds of PAHs in water were enriched by automatic solid-phase extraction using MIP-PAHs solid-phase extraction column as the carrier. The linear correlation coefficients of calibration curves for 16 PAHs in the linear range of 5.0-250 μg/L were all not less than 0.999 5. The limits of detection in this method for 16 PAHs were 0.89-1.97 ng/L, and the limits of quantification were 3.56-7.88 ng/L. Four actual water samples, including underground water, surface water, drinking water, and tap water, were determined according to the experimental method. The relative deviations of parallel samples were 0.11%-11.5%, and the spiked recoveries were 79.0%-123%. Samples of groundwater, surface water, drinking water, and tap water from the supply network with potential pollution risks around a coking plant were quantitatively analyzed.The relative standard deviations(RSD, n=7) of determination results were 1.9%-12%, and the spiked recoveries were between 71.5% and 119%.