The aim of the presented study was to elaborate a procedure for detecting and identifying organic accelerants in samples taken from the site of a fire. In the analysis of fire debris, a key-stage is the preparation of samples, encompassing separating of analytes from the matrix and concentrating them. In the elaborated procedure, head-space analysis with passive adsorption, followed by thermodesorption were used for the realisation of this stage. For the separation and the detection of analytes a gas chromatograph equipped with a flame-ionisation detector (FID) was used. Identification of analytes was performed on the basis of a comparison of the chromatograms gained with standard ones stored in the computer library.