A novel IL@PPPy-TiO2/NiOCNSs solid phase microextraction fiber was successfully fabricated by using 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid(IL) doped with polyphenylpyrrole(PPPy) onto the hydrothermally treated NiTi substrate with electrochemical deposition.The uniform and porous nanoparticles were coated on the surface of NiTi alloy.The extraction performance of the fiber was estimated by the combination of high performance liquid chromatography(HPLC)and itself using polychlorinated biphenyls(PCBs),phthalic acid ester(PAEs),polycyclic aromatic hydrocarbon(PAHs) and ultraviolet(UV) absorbent as model analytes.The novel IL@PPPy-TiO2/NiOCNSs fiber showed good extraction selectivity and high extraction capability toward PCBs in water samples.The effect factors including extraction temperature,stirring rate,extraction time and ionic strength on the extraction efficiency of PCBs were optimized.Under the optimized condition,there were linear relationships for the analytes in certain mass concentration range with correlation coefficients(r) not less than 0.998 6.The limits of detection(LOD) were in the range of 0.015-0.11 μg/L.The intra-day and inter-day relative standard deviations(RSD) for a single fiber were in the ranges of 4.7%-6.1% and 5.4%-7.0%,respectively.The fiber-to-fiber reproducibility(n=5) varied from 6.5% to 7.7%.Recoveries for 5 PCBs in real water samples ranged from 83.0% to 104% with RSD not more than 86%.The proposed SPME/HPLC method was successfully applied in the extraction and detection of trace PCBs in different water samples.