This paper describes the application of Headspace/Solid-Phase Microextraction/Gas Chromatography-Mass Spectrometry (HS/SPME/GC-MS) to the recovery and identification of volatile organic compounds in blood and viscera samples from decreased persons. The technique is used as a screening procedure to rapidly obtain information relating to toxicological investigations. The technique is suitable for the detection of volatiles (of wide boiling range) including butane, halothane, toluene, xylenes, and petrol residues in blood and viscera (lung, brain, and body fat).