Brominated diphenyl ethers (BDEs) are among the most important and most widely used flame retardants in a range of different industrial products. They are found worldwide in practically all types of matrices moving them into the focus of legislation[1,2]. Among the PBDE congeners decabromodiphenylether (BDE-209) became of particular trace analytical interest due to a discussed toxicological potential in the consequence of bioaccumulation. Due to its intrinsic properties very high boi領(lǐng) point combined with low thermal stability BDE-209 is difficult to analyze at residue levels. In this study chromatographic parameters including different injection techniques have been compared and optimized in order to achieve minimal thermal breakdown resulting in optimum achievable sensitivity. PTV on column injection is presented as a versatile alternative to a standard on column injector.