Ionic liquids found a wide application in catalysis and extraction due to their unique properties. Herein, ethylene glycol dimethacrylate as the cross-linker and 1-vinyl-3- butylimidazolium tetrafluoroborate as functional monomer via thermally initiated free-radical polymerization was prepared as a novel copolymer solid phase micro-extraction (SPME) coating. A surface modified stainless-steel wire was implemented as the substrate. Factors affecting the extraction performances of the copolymer, including the molar ratio of monomers to cross-linkers, the amount of porogen agent, and polymerization time were evaluated and optimized. To evaluate the extraction performance, five commonly seen polycyclic aromatic hydrocarbons (PAHs) were taken as the analytical targets. The potential factors affecting extraction efficiency were optimized. The as-prepared SPME device, coupled with gas chromatography, was successfully applied for the determination of PAHs in water samples. The wide linear range, low detection limit, good reproducibility, selectivity, and excellent thermal stability indicate the promising application of the newly developed SPME fiber in environmental monitoring as well as in other samples having complex matrices.