Abstract <p>This study aimed to develop a needle trap device (<b>NTD</b>) packed with a new molecularly imprinted polymer (<b>MIP</b>) extraction medium for the selective detection of <i>n</i>-hexane and methyl ethyl ketone (<b>MEK</b>) from exhaled air samples. Characterizations of the synthesized MIP were investigated by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, thermogravimetric analysis, and Brunauer–Emmett–Teller. Also, the optimization of desorption parameters such as time and temperature was performed by a central composite design-response surface methodology. First, extraction and determination of MEK and <i>n</i>-hexane were conducted by the proposed method on the laboratory scale and then used in a field study for shoe factory workers. Based on the results, the optimal desorption temperature and time were obtained at 190°C over 120 s, respectively. The analytical performance of NTD-MIP was confirmed by a recovery level &gt; 98.7% and precision by relative standard deviations between 2.06 and 8.05%. Furthermore, the limit of detection and the limit of quantitation of the NTD-MIP method were determined in the range of 0.024–0.020 and 0.080–0.069 ppm, respectively. It is worth mentioning that NTD-MIP showed a high analytical performance compared to the standard the National Institute for Occupational Safety and Health (NIOSH) method in all evaluated validation parameters. These results elucidated that the proposed NTD-MIP method can be employed as an eco-friendly, efficient, and selective procedure for monitoring <i>n</i>-hexane and MEK in exhaled air.</p>