Solid-phase microextraction (SPME) has rapidly been established among the practical alternatives for sample preparation for gas chromatography. Nevertheless polynuclear aromatic hydrocarbons (PAHs) are more effectively monitored by high-performance liquid chromatography (HPLC), but initially, there was no simple way to introduce analytes extracted by SPME into an HPLC system. A SPME-HPLC interface was developed by Supelco, which enables one to take advantages of the time and solvent savings offered by SPME. In the present work six PAHs from the European Union directives: fluoranthene, benzo[b]fluoranthene, benzo[k]fluoranthene benzo[a]pyrene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene were evaluated after optimization of a sample preparation method with a 100-micron poly(dimethylsiloxane) fiber. Repeatability, reproducibility, correlation coefficients, linearity, recoveries and limits of detection where determined and are indicated.