Addressing the challenge of accurately monitoring polycyclic aromatic hydrocarbons (PAHs) in aquatic systems, this study employed diffusive gradients in thin-films (DGT) technique to achieve methods detection limits as low as 0.02 ng L−1 to 0.05 ng L−1 through in situ preconcentration and determination of time-integrated concentrations. The efficacy of the developed DGT samplers was validated under diverse environmental conditions, demonstrating independence from factors such as pH (5.03–9.01), dissolved organic matter (0–20 mg L−1), and ionic strength (0.0001–0.6 M). Notably, the introduction of a novel theoretical approach to calculate diffusion coefficients based on solvent-accessible volume tailored for PAHs significantly enhanced the method’s applicability, particularly for organic pollutants with low solubility. Field deployments in coastal zones validated the DGT method against traditional grab sampling, with findings advocating a 4 to 7-day optimal deployment duration for balancing sensitivity and mitigating lag time effects. These results provide a sophisticated, efficient solution to the persistent challenge of monitoring hydrophobic organic pollutants in aquatic environments, broadening the scope and applicability of DGT in environmental science and providing a robust tool for researchers.