Trinitrobenzene (TNB) and trinitrotoluene (TNT) react in N,N-dimethylformamide (DMF) to form multiple species in solution. Despite structural similarities, electronic spectra show that the reactivity is different for TNB and TNT. In addition to reaction with the DMF solvent, residual water in nominally dry DMF generates sufficient hydroxide for reaction with TNB and TNT. Multiple sigma adducts are formed and observed to be fluorescent, which has not been previously reported. Both TNB and TNT show the capacity to form sigma adducts with hydroxide and DMF, while methyl hydrogens of TNT can be deprotonated by hydroxide.