Smoke inhalation remains a major cause of morbidity and mortality. Clinical and laboratory studies have revealed numerous potentially toxic components of combustion in the fire environment and in human tissue samples. However, the frequency and importance of the various compounds remains poorly understood. A new simple method to quantitatively measure volatile organic compounds (VOCs) in small samples of the blood of fire victims has been developed utilising the ‘purge and trap’ method of gas phase chromatography with flame ionisation detection using two columns. Thirty-three compounds were identified on the basis of the retention index method with acceptable repeatability and reproducibility. This method should permit a more complete investigation of the toxic volatile organic compounds found in fire victims.