A new SPME/HPLC interface is developed. It is based on thermal desorption from the SPME fiber and organic solvent collection of the desorbed analytes by sweeping them with an argon flow into a small organic solvent volume which is further injected into the HPLC chromatograph. Extraction and desorption parameters were investigated using five PAHs of different volatilities (naphthalene, acenaphthalene, fluorene, phenanthrene and anthracene) as test compounds and fluorimetric detection. Regression coefficients closed to 0.99 with RDS < 14% (n = 3) and detection limits in the range 0.07 - 0.99 μg.L^-1 were found. A method was applied to determine the above PAHs in water samples. The results were compared with those supplied by the 550.1 EPA method showing the agreement of both methods at the 0.05 significance level.