A novel dispersive liquid-liquid microextraction method based on solidification of floating organic droplets(DLLME-SFO) was developed for the determination of six kinds of chlorinated polycyclic aromatic hydrocarbons and fifteen kinds of polycyclic aromatic hydrocarbons in water samples by high performance liquid chromatography with fluorescence detection.The factors relevant to the microextraction efficiency,such as type and volume of disperant and extraction solvents,amount of NaCl and extraction time were investigated and optimized.The optimal liquid liquid microextraction experiment conditions were as follows:10 μL of 1 dodecanol as extractant solvent,500 μL of methanol as dispersive solvent,6%(mass percentage) NaCl,2 min of extraction time for vortex oscillation.The separation of the target compounds was performed on a SUPELCOSILTMLC-PAH column(150 mm×4.6 mm,5 μm) with acetonitrile-water as mobile phase by gradient elution.Quantitative determination was achieved by external standard method.Results showed that there existed good linear relationships for 21 target compounds in certain concentration ranges with their correlation coefficients(r) not less than 0.999.The average recoveries for the target compounds ranged from 70.6%to 98.7%with corresponding relative standard deviations(RSD,n=3) of 20%-10%.The limits of detection(LOD,S/N=3) and limits of quantification(LOQ,S/N=10) were in the ranges of 0.000 7-0.009 μg/L and 0.002 2-0.028 μg/L,respectively.The proposed method is applicable for the rapid determination of chlorinated polycyclic aromatic hydrocarbons and polycyclic aromatic hydrocarbons in surface water samples.