An explosive is an energetically unstable chemical material exploding upon initiation by friction, impact, shock, flame or any other simple application of an energetic pulse. Explosives are categorized according to various properties such as their rates of decomposition, structure and their utilization goal. Many papers on energetic materials have been published leading to the discovery of various types of compounds, which can be employed in propellants and explosive formulations. This review article focuses on the synthesis of benzofuroxan and their derivatives and on their energetic properties. Interestingly, investigation of structure-property relationships and use of theoretical studies highlight the structural evolution of energetic materials leading to higher performance, reduced sensitivity and improved chemical and thermal stability.