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Electrochemical synthesis serves as a green and efficient method with great application potential. However, it has not been extensively applied in the synthesis of energetic materials. Nitrogen-rich heterocyclic compounds, as a new generation of energetic materials, enjoy advantages such as eco-friendliness, high energy output, and excellent safety performance. This study reports the electrochemical cathodic synthesis of copper nitrotriazole [Cu(NTz)2] using copper chloride and 3-nitro-1,2,4-triazole as a reaction substrate and triethylamine as a deprotonation agent. The obtained Cu(NTz)2 comprises uniform spherical particles of nano lamellae. As the dosage of triethylamine increased from 50 μL to 150 μL, Cu(NTz)2 gradually grew into compact solid spherical particles, significantly increasing the energy output. Notably, the heat release increased from 711 J g−1 to 1301 J g−1, accompanied by a significant positive elevation of ignition performance and peak combustion pressure in the process of confined combustion. This greatly boosted the energetic performance of Cu(NTz)2. Moreover, Cu(NTz)2 demonstrates insensitivity to electrostatic discharge (E50＞225 mJ) and friction (FS＞360 N), suggesting excellent safety performance. Owing to its outstanding energetic and safety performance, Cu(NTz)2 boasts great potential for application as pyrotechnic compositions, including military gas-producing and incendiary agents. Moreover, it has been corroborated that Cu(NTz)2 can be applied as a micro ignitor.