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The requirements for the chemical to act as a primary explosive, its importance, and the hazards associated with heavy‐metal‐based primary explosives are all well‐stated in this review. In addition, it outlined the limitations of the heavy‐metal‐free primary explosives already in use. This analysis underlines the importance of green primary explosives with updated information. It summarizes the possible candidates of metal‐free new generation green primary explosives, including their preparation routes, energetic properties, applications, and comparisons to traditional primary explosives. Furthermore, this analysis also aims to discuss the necessity for metal‐free primary explosives as well as the significant problem of replacing traditional primary explosives. [ABSTRACT FROM AUTHOR]