Furoxan is a nitrogen-rich aromatic ring with a potential "nitro" fragment. The compactness of the skeleton and outstanding enthalpy of formation make it an important molecular skeleton for the research of energetic materials. The unique arrangement of nitrogen and oxygen atoms significantly increases the tendency of furoxan to tautomerism， and the presence of tautomers reduces the stability of the furoxan skeleton and increases the difficulty of its synthesis. This account reviews the research on the synthetic methodologies of furoxan based on different strategies. Focusing on the synthetic mechanism of furoxan framework itself， the advantages and disadvantages of different synthetic methodologies are analyzed and compared. Moreover， the progress of energetic materials based on the strategy developed for the synthesis of furoxan is also summarized. Considering the high density， high oxygen balance and high enthalpy of formation of furoxan ring， energetic structures based on the furoxans will still be a key direction of research and development of high energy density materials.