A headspace solid-phase dynamic extraction (HS-SPDE) technique was developed by the use of polypyrrole (PPy) sorbent, electropolymerized inside the surface of a needle, as a possible alternative to solid-phase microextraction (SPME). Thermal desorption was subsequently, employed to transfer the extracted analytes into the injection port of a gas chromatography–mass spectrometry (GC–MS). The PPy sorbent including polypyrrole-dodecyl sulfate (PPy-DS) was deposited on the interior surface of a stainless steel needle from the corresponding aqueous electrolyte by applying a constant deposition potential. The homogeneity and the porous surface structure of the coating were examined using the scanning electron microscopy (SEM). The developed method was applied to the trace level extraction of some polycyclic aromatic hydrocarbons (PAHs) from aqueous sample. In order to enhance the extraction efficiency and increase the partition coefficient of analytes, the stainless steel needle was cooled at 5 °C, while the sample solution was kept at 80 °C. Optimization of influential experimental conditions including the voltage of power supply, the time of PPy electrodeposition, the extraction temperature, the ionic strength and the extraction time were also investigated. The detection limits of the method under optimized conditions were in the range of 0.002–0.01 ng mL −1. The relative standard deviations (R.S.D.) at a concentration level of 0.1 ng mL −1 were obtained between 7.54 and 11.4% ( n = 6). The calibration curves of PAHs showed linearity in the range of 0.01–10 ng mL −1. The proposed method was successfully applied to the extraction of some selected PAHs from real-life water samples and the relative recoveries were higher than 90% for all the analytes.
