Advanced energetic materials (EMs) play a crucial role in the advancement of microenergetic systems as actuation parts, igniters, propulsion units, and power. The sustainable electrosynthesis of EMs has gained momentum and achieved substantial improvements in the past decade. This study presents the facile synthesis of a new type of high-performance CuN3@CuCl hybrids via a co-electrodeposition methodology utilizing porous Cu as the sacrificial template. The composition, morphology, and energetic characteristics of the CuN3@CuCl hybrids can be easily tuned by adjusting the deposition times. The resulting hybrids demonstrate remarkable energy output (1120 J·g-1) and good laser-induced initiating ability. As compared with porous CuN3, the uniform doping of inert CuCl enhances the electrostatic safety of the hybridized material without compromising its overall energetic characteristics. Notably, the special oxidizing behavior of CuCl gradually lowers the susceptibility of the hybrid material to laser and electrostatic stimulation. This has significant implications for the passivation or self-destruction of highly sensitive EMs. Overall, this study pioneers a new path for the development of MEMS-compatible EMs, facilitating further microenergetic applications.