The surface of a stainless‐steel wire was platinized using electrophoretic deposition method to create a high‐surface‐area with porous and cohesive substrate. The platinized fiber was coated by the polypyrrole/graphene oxide nanocomposite by electropolymerization and accommodated into a stainless‐steel needle to fabricate an in‐needle coated fiber. The developed setup was coupled to gas chromatography with flame ionization detection and applied to extract and determine polycyclic aromatic hydrocarbons (naphthalene, fluorene, phenanthrene, fluoranthene, and pyrene) in complicated solid matrices, along with reinforcement of the extraction by cooling the sorbent, using liquid carbon dioxide. To obtain the best extraction efficiency, the important experimental variables including extraction... temperature and time, temperature of cooled sorbent, sampling flow rate, and desorption condition were studied. Under the optimal condition, limits of detection for five studied analytes were in the range of 0.2–0.8 pg/g. Linear dynamic ranges for the calibration curves were found to be in the range of 0.001–1000 ng/g. Relative standard deviations obtained for six replicated analyses of 1 ng/g of analytes were 4.9–13.5%. The reinforced in‐needle coated fiber method was successfully applied for the analysis of polycyclic aromatic hydrocarbons in contaminated soil samples.