Abstract: Energetic materials, particularly explosives materials, are detected in samples by heating a mixture of a sample under a reduced pressure of not more than 100 mbar and detecting the chemiluminescent emission therefrom with a suitable light detector, for example a photomultiplier or photodiode. The sample is heated to a temperature in the region of from 300° C. to 500° C., conveniently in a quartz tube furnace placed within a vacuum chamber. The inlet to the tube furnace may be connected directly into the outlet from a gas chromatography apparatus such that individual compounds from a mixture may be detected as they pas sequentially through the chromatography apparatus and into the tube furnace. An inert carrier gas may be used such as nitrogen, argon or helium or a specific gas to enhance the responsiveness of the method for a particular sample material. Apparatus for carrying out the method is also provided.