Accelerants are substances that can initiate the emergence, accelerate fire, and spread fire. The most widely used accelerant is gasoline. In the case of intentionally fires, the primary task of the fire detection investigators is to find residues of flammable liquids and to take samples for laboratory analysis. Various detection means are used to search for combustible liquid residues. After transferring the collected samples to an accredited laboratory, the first step is to extract the flammable liquid from the recovered material, which is then analysed by various methods such as GC-MS, HS-GC-MS and HPLC. The measured data are evaluated and lead to the identification of the accelerator. Choosing an appropriate extraction technique is the first critical point in sample analysis. The aim of the work was to find out what extraction method and temperature during extraction will influence the accelerant yield from the fire samples. We compared two methods of extraction of the accelerants from the sample, namely HS and SPME. We also investigated how the extraction temperature affects the accelerants yield from fire samples.