Potassium fluoride,anhydrous
           Potassium fluoride,extra pure
           Potassium fluoride,Granular
           Silicon Dioxide
           Hydrofluoric acid
           Synthetic Cryolite
           Potassium Fluoaluminate
           Ammonium bifluoride
           Potassium Bifluoride
           Aluminium fluoride
           Sodium fluoride
           Potassium Fluorosilicate
           Fluorosilicic Acid
           Sodium silicofluoride
           Potassium Hydroxide Flakes
           Magnesium Fluoride
           Magnesium fluorosilicate
           Barium Fluoride
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Stainless steel wire has been widely used as the substrate of solid-phase microextraction (SPME) fibers to overcome the shortcomings of conventional silica fibers such as fragility, by many researchers. However, in previous reports various sorbent coatings are always required in conjunction with the stainless steel wire for SPME. In this work, we report the bare stainless steel wire for SPME without the need for any additional coatings taking advantage of its high mechanical and thermal stability. To evaluate the performance of stainless steel wire for SPME, polycyclic aromatic hydrocarbons (PAHs), benzene, toluene, ethylbenzene, chlorobenzene, n-propylbenzene, aniline, phenol, n-hexane, n-octane, n-decane, n-undecane, n-dodecane, chloroform, trichloroethylene, n-octanol, and butanol were tested as analytes. Although the stainless steel wire had almost no extraction capability toward the tested analytes before etching, it did exhibit high affinity to the tested PAHs after etching with hydrofluoric acid. The etched stainless steel wire gave a much bigger enhancement factor (2541?3981) for the PAHs than the other analytes studied (≤515). Etching with hydrofluoric acid produced a porous and flower-like structure with Fe2O3, FeF3, Cr2O3, and CrF2 on the surface of the stainless steel wire, giving high affinity to the PAHs due to cation?π interaction. On the basis of the high selectivity of the etched stainless steel wire for PAHs, a new SPME method was developed for gas chromatography with flame ionization detection to determine PAHs with the detection limits of 0.24?0.63 μg L?1. The precision for six replicate extractions using one SPME fiber ranged from 2.9% to 5.3%. The fiber-to-fiber reproducibility for three parallel prepared fibers was 4.3?8.8%. One etched stainless steel wire can stand over 250 cycles of SPME without significant loss of extraction efficiency. The developed etched stainless steel wire is very stable, highly selective, and reproducible for the SPME of PAHs.