A class of novel, environmental friendly ionic liquids (ILs) were synthesized by on-fiber preparation strategy and modified on graphene oxide (GO)-coated stainless steel wire, which was used as a solid-phase microextraction (SPME) fiber for efficient enrichment of polycyclic aromatic hydrocarbons (PAHs) and phthalate esters (PAEs). Surface characteristic of the ILs and polymeric-ILs (PILs) fibers with the wave-structure were inspected by scanning electron microscope. The successfully synthesis of bis(trifluoromethanesulfonyl)imide (NTf₂⁻)-based ILs were also characterized by energy dispersive spectrometer analysis. Through the chromatograms of the proposed two ILs (1-aminoethyl-3-methylimidazolium bromide (C₂NH₂MIm⁺Br⁻), C₂NH₂MIm⁺NTf₂⁻) and two PILs (polymeric 1-vinyl-3-hexylimidazolium bromide (poly(VHIm⁺Br⁻)), poly(VHIm⁺NTf₂⁻))-GO-coated fibers for the extraction of analytes, NTf₂⁻-based PIL demonstrated higher extraction capacity for hydrophobic compounds than other as-prepared ILs. Analytical performances of the proposed fibers were investigated under the optimized extraction and desorption conditions coupled with gas chromatography (GC). Compared with the poly(VHIm⁺Br⁻)-GO fiber, the poly(VHIm⁺NTf₂⁻)-GO SPME fiber brought wider linear ranges for analytes with correlation coefficient in the range of 0.9852–0.9989 and lower limits of detection ranging from 0.015–0.025 μg L⁻¹. The obtained results indicated that the newly prepared PILs-GO coating was a feasible, selective and green microextraction medium, which could be suitable for extraction and determination of PAHs and PAEs in potatoes and food-wrap sample, respectively.