Three kinds of adsorbant solid phase microextractions (SPME) were used to study the gases released from aged JOB explosives. These gases were obtained by storing the explosives in a closed vessel and heating them for a certain period of time. The extraction and adsorption properties of these SPMEs and the qualitative identification of the gas components have been examined by using SPME coupled with GC/MS analytical techniques. The results show that SPMEs can adsorb selectively and preconcetrate the trace organic volatiles (such as solvents, impurities) and some inorganic gases from explosives and its pertinent materials aged at different conditions. Furthermore, the ageing mechanism of JOB explosives was also explored.