Novel unbreakable solid phase microextraction (SPME) fiber coatings were fabricated by electrospinning method in which the polymeric solution was converted to nanofibers using high voltages. Four different polymers, polyurethane (PU), polycarbonate (PC), polyamide (PA) and polyvinyl chloride (PVC) were prepared as the fiber coatings on thin stainless steel wires. The extraction efficiencies of new coatings were investigated by headspace solid-phase microextraction (HS-SPME) of some environmentally important chlorobenzenes from aqueous samples followed by gas chromatography-mass spectrometry (GC-MS) analysis. Among them, PU showed a prominent efficiency. Effects of coating time and polymer concentration on the PU fiber capability were also optimized. The scanning electron microscopy (SEM) images of the PU coating showed a diameter range of 150–600 nm with a homogeneous and porous surface structure. Effects of different parameters influencing the extraction efficiency including the extraction temperature, extraction time, ionic strength, desorption temperature and time were investigated and optimized. The limits of detection and quantification of the method under optimized conditions were 10 and 50 ng L⁻¹, respectively. The relative standard deviations (RSD) at a concentration level of 0.5 ng mL⁻¹ were obtained between 3 and 8% (n = 3). The calibration curves of CBs showed linearity from 50 to1000 ng L⁻¹. The proposed method was successfully applied to the extraction of CBs from real water samples and relative recoveries were between 94 and 102%.