As a new initiation technology， laser initiation can effectively solve the safety problems existing in traditional initiation methods， such as stray current interference. As the energy output carrier in laser initiation sequence， the laser-sensitive primary explosive is an important part of the laser initiation system. At present， complex laser-sensitive primary explosive has becomes a research hotspot. The synthesis of energetic complexes with chain nitrogenous compounds， triazole， tetrazole， and tetrazine as ligands and the development status of laser initiation properties were summarized. The advantages and existing problems of various agents were analyzed， some laser initiation mechanisms were summarized， and the development of new laser-sensitive primary explosives in the future was prospected. It is pointed out that the development of new nitrogen-rich ligands is still an important direction for the future research of laser sensitive energetic complex primary explosives.