The application of single photon ionization in combination with mass-selective detection by time-of-flight mass spectrometry is described for the rapid detection of the nitro-containing explosives and explosives-related compounds nitrobenzene, 1,3-dinitrobenzene, o-nitrotoluene, 2,4-dinitrotoluene, and 2,4,6-trinitrotoluene, as well as the peroxide-based explosive triacetone triperoxide in the gas phase. The technique is demonstrated to be a plausible approach for laser-based rapid detection of explosives. The limits of detection for nitrobenzene and 2,4-dinitrotoluene using SPI were also measured and determined to be 17-24 (S/N approximately 2:1) and approximately 40 ppb (S/N approximately 2:1), respectively.