Polynitroaromatics are well-known to form anionic σ-complexes (Meisenheimer complexes). The formation of such complexes was assumed in the past to explain the blue color of solutions of 2,4-dinitrotoluene (DNT) and amines. However, this work shows that caution is warranted to avoid the hasty misidentification of Meisenheimer complexes. (1)H NMR spectra exhibit no significant shifts in the positions of the DNT protons, indicating that the majority of DNT species in solutions of DNT and amines retain their aromaticity. Density functional calculations on DNT-ethylamine complexes suggest that Meisenheimer complexes are sufficiently high in free energy so that they make up only a very small fraction of the full equilibrium population. While principal component analysis of the UV/vis spectra of the DNT-amine solutions reveals that only one absorbing species of significant concentration is formed, quantitative fits of Job's plots show that 1:1 association of DNT with the amines alone cannot explain the visible absorption spectra. Instead, the Job's plots can be accurately interpreted by deprotonation of DNT, with the amines acting as bases. The deprotonation equilibria lie far on the side of the unreacted DNT, preventing the detection by NMR of the deprotonated minority species that gives the solutions their strong blue color. The analysis of systems with DNT and n-butylamine, diethylamine, triethylamine, or benzylamine provides a consistent pK(a) of DNT in dimethyl sulfoxide of 15.3 ± 0.2.