In this work, solid-phase microextraction coupled with gas chromatography–mass spectrometry was developed to determine trace levels of nitrobenzene compounds in water and soil samples. Graphene was chosen as the extraction material and its composite was coated on a stainless steel wire through sol–gel technique for the solid phase microextraction. The key parameters influencing the extraction efficiency were optimized. Under the optimal conditions, the linearity for the compounds was observed in the range of 0.02–15.0 mg/L for water samples, and 0.2–60.0 mg/kg for soil samples, with the correlation coefficients(r) of 0.9966–0.9987. The limits of detection of the method were 0.0025–0.005 mg/L for water samples, and 0.02–0.04 mg/kg for soil samples. The recoveries for the spiked samples were in the range of 72.0%–113.2%, and the precision, expressed as the relative standard deviations, was less than 12.1%. In this work, solid-phase microextraction coupled with gas chromatography-mass spectrometry was developed to determine trace levels of nitrobenzene compounds in water and soil samples. Graphene was chosen as the extraction material and its composite was coated on a stainless steel wire through sol- gel technique for the solid phase microextraction. The key parameters influencing the extraction efficiency were optimized. Under the optimal conditions, the linearity for the compounds was observed in the range of 0.02-15.0 mg / L for water samples, and 0.2-60.0 mg / kg for soil samples, with the correlation coefficients (r) of 0.9966-0.9987. The limits of detection of the method were 0.0025-0.005 mg / L for water samples, and 0.02-0.04 mg / kg for soil samples. The recoveries for the Spiked samples were in the range of 72.0% -113.2%, and the precision, expressed as the relative standard deviations, was less than 12.1%.