In connection with medicolegal autopsies peripheral blood (e.g. from a femoral vein) is the specimen of choice for toxicological analysis, although alternative specimens are also sometimes submitted, such as bile, cerebrospinal fluid (CSF), vitreous humor (VH), bladder urine, pleural effusions and/or lung fluid. Ethanol concentrations were determined in duplicate in femoral blood and in various alternative biological specimens by headspace gas chromatography. The analysis was carried out on two different fused silica capillary columns furnishing different retention times for ethanol and both n-propanol and t-butanol were used as internal standards. The results were evaluated by linear regression using blood alcohol concentration (BAC) as dependent or outcome variable and the concentrations in an alternative specimen as independent or predictor variable. The Pearson correlation coefficients were all statistically highly significant (P < 0.001); r = 0.94 (bile), r = 0.98 (CSF), r = 0.97 (VH), r = 0.92 (urine), r = 0.94 (lung fluid) and r = 0.96 (pleural cavity effusions). When the regression model was used to predict femoral BAC from the mean concentration in an alternative specimen the mean and 95% prediction intervals were 1.12 ± 0.824 g/L (bile), 1.41 ± 0.546 g/L (CSF), 1.15 ± 0.42 g/L (VH), 1.29 ± 0.780 g/L (urine), 1.25 ± 0.772 g/L (lung fluid) and 0.68 ± 0.564 g/L (pleural cavity effusions). This large uncertainty for a single new observation needs to be considered when alcohol-related deaths are evaluated and interpreted. However, the analysis of alternative specimens is recommended in medical examiner cases to provide supporting evidence with regard to the origin of ethanol, whether this reflects antemortem (AM) ingestion or postmortem (PM) synthesis.