The thermal stability of a set of aliphatic nitroalkanes, comprising primary and secondary nitroalkanes, with short and long linear chains or cyclic, was tested by differential scanning calorimetry (DSC) analysis, for comparative purposes. An exothermic decomposition phenomenon of a high entity occurred for all compounds, and no significant difference was observed to depend on the structure of the compounds tested. A maximum recommended process temperature (T D24 ) to avoid decomposition is estimated for the studied compounds. Although estimated T D24 values are difficult to access under normal conditions of handling and storage in R&D labs, the decomposition energy for all the compounds is higher than 500 J/g, and thus, attention should be paid, especially for transportation, storage, and handling. Yoshida correlation and a more conservative modified correlation developed by Pfizer were applied to the DSC data to predict shock sensitivity and explosive propagation. With the most used Yoshida correlation, some nitroalkanes are predicted to be potentially shock sensitive and explosive as neat substances. Pfizer-modified correlation flags all the compounds to be potentially explosive or shock-sensitive. The information provided herein indicates the inherent reactivity of these compounds and could provide suggestions about precautions for storage and handling in a R&D laboratory. In light of this information, it is advisable to run accelerating rate calorimetry evaluation and experimental explosive testing to complete the hazard assessment before employment on an industrial scale.