In the present work, a new solid phase microextraction (SPME) fiber coating based on modified silica-polyamide (PA) nanocomposite was electrospun on a stainless steel wire. Four modified silica-PA nanocomposites together with PA were fabricated by dispersing several typical modified silica nanoparticles in PA polymer solution prior to electrospinning. The surface characteristic of PA nanofibers and modified silica-PA nanocomposites was investigated using scanning electron microscopy (SEM). The homogeneity and the porous surface structure of the modified silica-PA nanocomposites were confirmed by SEM, showing nanofibers diameters lower than 170 nm. The applicability of the new fiber coating was examined by headspace SPME of some selected chlorobenzenes (CBs), as model compounds, from aqueous samples. Subsequently, the extracted analytes were transferred into a gas chromatography (GC) by thermal desorption. Influencing parameters on the morphology of nanocomposites such as type of modified silica nanoparticles and the weight ratio of components were optimized. In addition, effects of different parameters influencing the extraction efficiency including extraction temperature, extraction time, ionic strength, desorption temperature, and desorption time were investigated and optimized. Eventually, the developed method was validated by gas chromatography-mass spectrometry (GC-MS). At the optimum conditions, the relative standard deviation values for a double distilled water spiked with the selected CBs at 100 ng L-1 were 4-12% (n = 3) and the limit of detection for the studied compounds was between 5 and 30 ng L-1. The calibration curves of analytes were investigated in the range of 50-1000 ng L-1 and correlation coefficients (R-2) between 0.9897 and 0.9992 were obtained. (C) 2013 Elsevier B.V. All rights reserved.