A polymeric ionic liquid modified stainless steel wire for solid-phase microextraction was reported. Mercaptopropyl-functionalized stainless steel wire that was formed by co-condensation of tetramethoxysilane and 3-mercaptopropyltrimethoxysilane via a sol-gel process, which is followed by in situ surface radical chain-transfer polymerization of 1-vinyl-3-octylimidazolium hexafluorophosphate to result in polymeric ionic liquid modified stainless steel wire. The fiber surface was characterized by field emission scanning electron microscope equipped with energy dispersive X-ray analysis. Coupled with GC, extraction performance of the fiber was tested with phenols and polycyclic aromatic hydrocarbons as model analytes. Effects of extraction and desorption conditions were investigated systematically in our work. RSDs for single-fiber repeatability and fiber-to-fiber reproducibility were less than 7.34 and 16.82%, respectively. The calibration curves were linear in a wide range for all analytes and the detection limits were in the range of 10–60 ng L−1. Two real water samples from the Yellow River and local waterworks were applied to test the as-established solid-phase microextraction–GC method with the recoveries of samples spiked at 10 μg L−1 ranged from 83.35 to 119.24%. The fiber not only exhibited excellent extraction efficiency, but also very good rigidity, stability and durability.