A general method for the trace analysis of benzodiazepine drugs and their major metabolites at single dose therapeutic levels in 0.2 ml blood samples is described. The method involves solvent extraction of blood with toluene, isolation of the analytes using deactivated Amberlite XAD-7 porous polymer beads, and analysis of the cleaned-up extracts by capillary column gas chromatography with electron-capture detection. The clean-up technique eliminates lipids and other interfering material, enabling routine analysis of blood extracts to be carried out with no significant deterioration in column or detector performance over a period of many months. The use of fused-silica capillary columns coated with SE-52 and the correct choice of chromatographic conditions permits underivatised benzodiazepines of widely differing volatilities and polarites to be analysed. Data for 26 benzodiazepines and metabolites are presented.