Abstract The identification and characterization of smokeless powders by means of gas chromatographic examination of their pyrolysis products is possibly the most significant method of selective identification available to the forensic examiner. Minor constituent analysis has been established as a rapid and accurate means of distinguishing various powders from each other [1], but the inherent limitations resulting from the amount of sample necessary for examination and the chemical changes associated with the burning of surface coatings restrict the utility to situations where grains of virtually unaltered powder can be obtained. The examination of powders by thermoanalytical methods [2,3] introduces the advantage of reduced sample size, but these techniques are not so selective and have limitations when partially burned powder is being examined. Pyrolysis gas chromatography, on the other hand, is advantageous in that it requires only small samples and the examination is primarily of homogeneous constituents that exhibit considerable variations among different lots of powder.