2,4,6-Trinitrotoluene is a high explosive that has been used for military purposes since 1902. Ammunition manufacturing facilities where TNT is made as well as sites across the world used to test military explosives in diverse ways, such as landmines and unexploded ordnance that have been buried in soil; grenades, etc are concerned with the health hazard and environmental problem of TNT. Since TNT is a contaminant that remains in the soil and produces various carcinogenic compounds as a result of photodecomposition and biodegradation, large amounts of the nitroaromatic compounds represent both a threat and a problem. Vibrational spectroscopy is a powerful tool that can be used to characterize TNT in its diverse condensed forms: droplets and crystals of polymorphs. Crystallization of TNT from different solvents: water, methanol, chloroform, acetone, and acetonitrile, was carried out and the vibrational spectra were obtained during crystallization. Crystals produced from evaporation of the mentioned solvent showed a similar crystallization pattern, and their spectroscopic information obtained was found to depend on the physical form of TNT. The nitroaromatic compound exhibits a series of unique characteristic bands that allow its detection and spectroscopic characterization. The spectroscopic signatures of neat TNT samples were determined with Raman Microspectroscopy and used as comparison standards. Strong bands about 1365 and 2956 cm-1 dominate the Raman spectrum of neat TNT. The intensity and even the presence of these bands are found to be remarkably dependent on TNT form and source.