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A new method for the determination of 4 EDCs (bisphenol A, 17-β-estradiol, estrone and diethylstilbestrol) in water samples has been developed by using polypropylene hollow fiber supported ionic liquid (IL, 1-Octyl-3-methylimidazolium hexafluorophosphate, [C8MIM][PF6]) microextraction (HF-LPME) combined with HPLC/UV, which was applied to investigate the pollutions in surface water at Neijiang River located at Zhenjiang, Jiangsu Province.To achieve the optimum extraction efficiencies, several main parameters were investigated.Under the optimal extraction conditions (sample pH, 2.0; volume of extraction solvent, 2.5 μL; ionic strength, 2.57) the proposed method offered: good linearity range, 0.15~100μg L-1, with the correlation coefficients (r2) of 0.9996, 0.9994, 0.9990 and 0.9984, respectively; low LOD, 0.03, 0.05, 0.10, 0.05 μg L-1 (S/N=3) for bisphenol A, 17-β-estradiol, estrone and diethylstilbestrol, respectively; good reproducibility (relative standard deviation, RSD, 8.41%, 7.61%, 9.00%, 7.22%, respectively, n=5); satisfied recoveries (80.2-107.1%, n=5); high enrichment factor, 5240, 3693, 2425 and 2086 for the four chemicals, respectively.Using the proposed HF-LPME, among 15 sampling sites along Neijiang River, bisphenol A, diethylstilbestrol and 17-β-estradiol were detected in some sites, all which were the near suburban sampling sites.The result indicated that the role of municipal sewage is an important source of EDCs contamination.