A simple needle-trap device (NTD) coupled with gas chromatography-mass spectrometry (GC-MS) was developed to determine trace levels of nitrobenzenes (NBs) in workplace air. The NTD with sorbent inside the needle was employed for the quantification of nitrobenzene, o-nitrotoluene, m-nitrotoluene, p-nitrotoluene, o-nitrochlorobenzene, m-nitrochlorobenzene, and p-nitrochlorobenzene. The optimum temperature and time for desorption of analytes were 270 °C and 4 min, and parameters such as sampling flow rate, breakthrough volume, and storage capability were also optimized. The limits of detection and quantification were in the ranges of 1.8 × 10−4–1.1 × 10−3 and 5.9 × 10−4–3.6 × 10−3 mg m−3, respectively. The developed protocol was successfully applied for the determination of NBs in vehicle repair plants where the highest detected concentration was 0.11 mg m−3. The established NTD-GC-MS generally applies to monitoring trace levels of NBs in the air.