Thermal desorption (TD) of wipe-based samples was coupled with an in-line dielectric barrier discharge ionization (DBDI) source and rugged compact time-of-flight mass spectrometer (MS) for the detection of explosives, propellants, and postblast debris. The chromatography-free TD-DBDI-MS platform enabled rapid and sensitive detection of organic nitramine, nitrate ester, and nitroaromatic explosives as well as black powder and black powder substitute propellants. Parametric investigations characterized the response to TD temperature and optimized DBDI voltage, aerodynamically assisted entrainment, and fragmentation through in-source collision induced dissociation (isCID). Excess nitrate generated by the DBDI source yielded predominantly nitrate-adduct formation. Subnanogram sensitivities were demonstrated for all explosives investigated, except for nitroglycerin, specifically due to its volatility. Further, most analytes/explosives exhibited tens of picograms sensitivities. The platform also demonstrated the detection of propellant and military explosives from postblast debris. The TD-DBDI-MS system performed well without the need for aerodynamically assisted entrainment (and the associated rough pump), which along with requiring no additional gases (i.e., N2 or He) or solvents, aid in potential field deployment. The ease of TD-DBDI attachment and removal added trace solid or liquid residue detection to the rugged mass spectrometer, designed primarily for the analysis of volatile organic and inorganic compounds.