This paper reports a comparison study of headspace sampling with microextraction devices for detecting an accelerant such as motor gasoline from fire debris collected at the fire scene. Microextraction devices compared solid-phase microextraction (SPME) device and improved gastight syringe. This microextraction device is made from 250 μL volume gastight syringe and 6-cm length GC column. The inside of this short GC column is mounted with an activated charcoal powder. Extraction procedure is performed by the strokes of the plunger in this microextraction gastight syringe (MEGS). The extraction of volatile organic compounds with MEGS is the same as the principle of the dynamic headspace concentration with an absorption tube. Compared to SPME, MEGS is a practical device for headspace sampling of volatile organic compounds with high concentration capability.