The authors introduce an arc ion plating method for the deposition of chromium oxide (Cr₂O₃) on a steel wire substrate, and its use as a coating for solid phase microextraction. The coating has a micro- and nano-scaled structure after annealing at 700 °C. It is found that Cr₂O₃ exhibits a good extraction capability for the aromatic hydrocarbons naphthalene, anthracene, fluorene, fluoranthene, and biphenyl. Following desorption by high temperature at 300 °C, the analytes were quantified by gas chromatography (GC). The limits of detection are in the range between 20 and 200 ng·L⁻¹, and calibration plots are linear within a wide range (0.2 to 400 μg·L⁻¹). The coating has excellent mechanical properties, with a hardness is as high as 31.7 GPa, and the adhesion strength between coating and substrate reaches 20.1 N (corresponding to the critical Hertzian contact stress of 10 GPa). This, along with the chemical and thermal stability of the Cr₂O₃ coating, endows the wire with a long operational life. It was used for at least 100 times without any obvious decline of extraction capability.