In this study, a novel functionalized electrospun nanofibrous material was developed through a straightforward and robust approach that combines polydopamine (PDA) mediation and hydrothermal growth. This material was utilized as a SPME probe for polycyclic aromatic hydrocarbons (PAHs) analysis. Under optimal extraction conditions, the proposed method exhibited higher enrichment factors (1362–4563) and lower detection limits (0.003–0.35 ng mL−1), with relative standard deviations (RSDs) below 6.7 %. Applied to water samples, the stability and reproducibility of the nanofibrous have been validated with the intra- and inter-assay RSD in 2.3–9.8 % and 1.5–9.9 %, respectively. Acceptable recoveries of 87.1–109.2 % were achieved. Furthermore, the developed SPME-GC method was successfully applied to the analysis of PAHs in water samples.