Ion mobility spectrometry (IMS) is a rugged, inexpensive, sensitive, field portable technique for the detection of organic compounds. It is widely employed in ports of entry and by the military as a particle detector for explosives and drugs of abuse. Solid phase microextraction (SPME) is an effective extraction technique that has been successfully employed in the field for the pre-concentration of a variety of compounds. Many organic high explosives do not have a high enough vapor pressure for effective vapor sampling. However, these explosives and their commercial explosive mixtures have characteristic volatile components detectable in their headspace. In addition, taggants are added to explosives to aid in detection through headspace sampling. SPME can easily extract these compounds from the headspace for IMS vapor detection. An interface that couples SPME to IMS was constructed and evaluated for the detection of the following detection taggants: 2-nitrotoluene (2-NT), 4-nitrotoluene (4-NT), and 2,3-dimethyl-2,3-dinitrobutane (DMNB). The interface was also evaluated for the following common explosives: smokeless powder (nitrocellulose, NC), 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), 2,4,6-trinitrotoluene (2,4,6-TNT), hexahydro-1,3,5-trinitro-s-triazine (RDX), and pentaerythritol tetranitrate (PETN). This is the first peer reviewed report of a SPME-IMS system that is shown to extract volatile constituent chemicals and detection taggants in explosives from a headspace for subsequent detection in a simple, rapid, sensitive, and inexpensive manner.