Thermal degradation of soft wheat, durum wheat, and maize as well as native starch and maize dextrin used to make ﬁreworks, under nitrogen atmosphere, was studied by differential scanning calorimetry and thermo- gravimetric analysis. The results indicate that bran-free products give rise to a decomposition via transglycosyla- tion-volatilization. On the contrary, wheat products con- taining bran or ligno-cellulosic residues decompose via exothermic reaction of dehydration-charring. For each product, the curve is determined as a function of its physical form, i.e., ﬂour, ground product, and grain. The comparison of the conversion calculated as a ﬁrst-order kinetics and the experimental, exhibits a very low mean square error. On this basis, the pyrolysis was assumed to obey ﬁrst-order kinetics. The kinetic results were then used to estimate the temperature of spontaneous combustion, when these pro- ducts are stored in silos. In particular, Frank-Kamenetskii theory is applied to prove how the products, under particular conditions, can become extremely explosive.