The potential of supercritical fluid chromatography (SFC) coupled on-line to solid-phase extraction (SPE) with disks for determining sixteen different polycyclic aromatic hydrocarbons (PAHs) was assessed. A preliminary study of the chromatographic separation was conducted that led to the use of SPE coupled to SFC for improved detection limits. Disks of two different materials, i.e., C 18 and polystyrene-divinylbenzene, were assayed in terms of the variables influencing the extraction step. C 18 disks provided the best results, with detection limits ranging from 0.1 to 1.5 μg l −1 . The ensuing method was applied to river and tap water, with good repeatability and reproducibility, and no interference from the sample matrix.