Dichloroglyoxime is an efficient industrial bactericide and an important starting material for construction of nitrogen heterocyclic framework， which can be utilized as a pivotal precursor for a variety of high nitrogen energetic materials with excellent performances. Three synthetic methods of dichloroglyoxime， such as chlorine method， NCS/DMF method and NCS/DMF improved method， were introduced， and their advantages and disadvantages were also discussed. Based on the reaction characteristics of dichloroglyoxime， the methods of constructing N-heterocyclic frameworks， such as isoxazole，furoxan， furoxan， bistetrazole and oxadiazolone， were systematically described. Additionally， the physicochemical properties and detonation performances of typical energetic materials were also discussed. Using dichloroglyoxime as starting materials， it is expected to design and synthesize some new energetic materials with excellent performances，and comprehensively promote the innovation ability of energetic materials.