In this study, a needle trap extraction device with a molecularly imprinted polymer coated on Dupont fibers was developed for extraction. A number of heat-resistant Dupont fibers were longitudinally filled into a glass capillary, followed by coating with a molecularly imprinted polymer as an extraction medium and were used to extract volatile organic compounds from environment. Subsequently, the extracted analytes were analyzed by gas chromatography. The linear detection range, recovery, limit of detection (LOD), limit of quantification (LOQ) was studied to evaluate the method. Calibration curves for benzene, toluene, ethylbenzene, and o-xylene were linear in the concentration range of 1-250 μg/L, and the corresponding correlation coefficients exceeded 9897. The LODs and LOQs of the analytes were in the ranges of 15-25 ng/L and 35-65 ng/L, respectively.