The headspace solid phase microextraction method with modified silica fibers prepared based on self assembled gold nanoparticles and the sol–gel method is described for the determination of trace amounts of polycyclic aromatic hydrocarbons in environmental water samples using high performance liquid chromatography-UV detection. Extraction parameters such as extraction time, extraction temperature, desorption time, type and volume of desorption solvent, sample volume and ionic strength were evaluated and optimized by experimental design. At the optimum specified conditions, a high characteristic performance such as reproducibility, repeatability, a linear range (1–500 ng mL⁻¹) along the reasonable determination coefficient up to 0.995, and the presence of a low limit of detection (from 0.10 to 0.89 ng mL⁻¹) suggest good and efficient applicability of the method for estimation and quantification of the analytes under study. The proposed method was successfully applied for the extraction of polycyclic aromatic hydrocarbons in various environmental samples with relative recoveries for the spiked samples at 50 ng mL⁻¹ of analytes in the range of 84 to 106% and RSDs below 5.1%. Also, the reproducibilities of the fibers were in the range of 1.2–3.9, and the reproducibilities between fibers were in the range of 3.6–6.7.