It is shown that 2, 4, 6-Trinitrotoluene (TNT) displays strong and distinct structures in differential reflectograms, near 420 nm and 250 nm. These characteristic peaks are not observed from approximately two dozen organic and inorganic substances which we tested and which may be in or on a suitcase. This exclusivity infers an ideal technique for explosives detection in mass transit and similar locations. The described technique for detection of explosives is fast, inexpensive, reliable, portable, and is applicable from some distance, that is, it does not require contact with the surveyed substance. Moreover, we have developed a curve discrimination program for field applications of the technique. Other explosives such as 1, 3, 5-trinitro-1, 3, 5 triazacyclohexane (RDX), 1, 3, 5, 7-Tetranitro-1, 3, 5, 7-tetraazacyclooctane (HMX), 2, 4, 6, N-Tetranitro-N-methylaniline (Tetryl), Pentaerythritol tetranitrate (PETN), and nitroglycerin have also been investigated and demonstrate similar, but unique, characteristic spectra. The technique utilizes near-ultraviolet to visible light reflected from two spots on the same sample surface yielding a differential reflectogram corresponding to the absorption of the sample. The origin of the spectra is attributed to the highest occupied molecular orbital to lowest unoccupied molecular orbital (HOMO-LUMO) transitions of the respective explosive molecule. Experiments using transmission spectrophotometry have also been performed to compliment and confirm the specific transitions. The results are supported by computer modeling of the molecular orbitals that yield UV and visible transitions.