This paper presents the result of an investigation of the potential use of solid-phase microextraction (SPME) as a tar sampling method. The SPME stationary phase used was 50 mu m of polydimethylsiloxane (PDMS) coated on a fused silica fiber. Tar model compounds normally present in a producer gas from gasifiers, benzene, toluene, indane, indene, naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, and pyrene, were used in the investigation. The adsorbed compounds were analyzed by injection into gas chromatography coupled to a flame ionization detector (GC- FID). The amount of adsorbed tar on the SPME fiber determined the detection and quantification limits for the method. The results showed that adsorption of tar model compounds on the SPME fiber increased with decreasing polarity. The adsorption of compounds increased with a decreasing temperature, enabling a possibility to tune the sensitivity of the method by changing the sampling temperature. Conclusively, SPME has a very high potential as a tar sampling method and, in combination with GC- FID trace analysis of tar, is a feasible application.