Abstract In this study, a Raman spectrum of TNT was characterized through experiments and simulated using 22 hybrid density functional theory (DFT) methods. Among the different hybrid DFT methods, it was found that the most accurate simulation results of the Raman shift frequency were calculated by the O3LYP method. However, the deviations of the calculated Raman frequencies from the experimental value showed no dependency on the abilities of the DFT methods in recovering the correlation energy. The accuracies of the DFT methods in predicting the Raman bands are probably determined by the numerical grid and convergence criteria for optimizations of each DFT method. It was also decided that the prominent Raman shift 1362 cm −1 is mainly caused by symmetric stretching of the 4-nitro groups. Findings of this study can facilitate futuristic development of more effective surface enhanced Raman spectroscopy/scattering (SERS) substrates for explosive characterization and detection.