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., C18 and polystyrene-divinylbenzene, were assayed in terms of the variables influencing the extraction step. C18 disks provided the best results, with detection limits ranging from 0.1 to 1.5 micrograms l-1. The ensuing method was applied to river and tap water with good repeatability and reproducibility, and no interference from the sample matrix.