The chemical analysis of fire debris for traces of ignitable fuels is both problematic and complex. 1–9 Arson investigators have proposed various solutions based on identification of the accelerant, 3, 10 matrix effects, 11, 12 interferences of pyrolytic products, 13, 14 a comparison with inadequate standard chromatograms, 15, 16 the low content of target compounds, the tedious preliminary sample manipulation17 and the timedependant modification of the accelerant chromatographic profile. 18Many extraction techniques have been used to minimize the negative effects mentioned above, including passive adsorption/thermal desorption and solvent extraction, 17 headspace19 and solid-phase micro-extraction. 20–22 All of these extraction techniques when coupled with gas chromatography (GC)–mass spectrometry (MS) give results that, in the majority of instances, are sufficient to identify the original accelerant. 23 Further improvements applied to certain method phases or components increase the performance of the method. 24–31 The aim of this study was to optimize the thermal desorption cold trap (TCT) extraction process, followed by the recovery of specific chromatographic profiles and digital parameters by GC–MS, so as to verify the sensitivity and specificity of the accelerant analysis method. A flow chart pathway made identifying the nature and conditions of any studied accelerant easier.