A molecularly imprinted polymer with trinitrotoluene as the template molecule was synthesized and used as the novel coating for solid-phase microextraction of the nitroaromatic explosive 2,4,6-trinitrotoluene for its selective determination. The fiber was characterized in terms of coating thickness, morphology, intra- and inter-batch repeatability and extraction efficiency. An average thickness of 50 ± 4 μm with a uniform distribution of the coating was obtained. Good performances of the developed procedure in term of both intra-batch and inter-batch repeatability with relative standard deviations <8% were obtained. Finally, detection and quantitation limits in the low nanogram per kilogram levels were achieved proving the superior extraction capability of the developed coating, obtaining gas chromatography-mass spectrometry responses about two times higher than those achieved using commercial devices.