Polyvinylidenefluoride (fluorocarbon polymer sorbent) with surface area 8.4m 2 g −1 and particle size 15–30μm was used for on-line SPE–HPLC determination of naphthalene, biphenyl, acenaphthene, anthracene and pyrene in natural water. Desorption eluent flow rates were varied from 0.50 to 1.75mlmin −1 and the volume of analyte-containing eluent stream zone was 0.10–0.11ml, while empty preconcentration column volume is 0.10ml. Detection limits of SPE–HPLC method were established: 5ngl −1 (biphenyl), 7ngl −1 (anthracene), 8ngl −1 (acenaphthene), 30ngl −1 (pyrene), 40ngl −1 (naphthalene), using UV spectrophotometric detection. Several samples of natural and potable water were spiked with mixture of PAHs, thus validating the proposed technique.