Jingwei Li, Zhichao Zhao, Yihao Shen, Yongsheng Jia, Jinshan Sun, Yingkang Yao, Quanmin Xie, Yurong Liu, Guangyu Yin, Zhangbo Ming, Xuwen Liu
Abstract The practical application of Metastable Intermolecular Composites (MICs) has long been constrained by an intrinsic trade‐off: the high specific surface area required for rapid energy release inevitably induces extreme sensitivity and structural fragility, while conventional stabilizing additives compromise energy density. To resolve this, we present a bio‐inspired geometric‐interfacial nanoarchitectural strategy. Hierarchically ordered films were engineered via the oriented assembly of 2D flake aluminum (F‐Al) and flake copper oxide (F‐CuO) into a nacre‐mimetic “brick‐and‐mortar” architecture. This design enhances stimulus‐specific response: edge stress concentration in F‐Al reduces thermal ignition thresholds by >40%, while percolating conductive networks increase electrostatic safety by 73%. Mechanically, the architecture improves strength and toughness by >300% through crack deflection and frictional dissipation. Furthermore, energy release efficiency is amplified, achieving an 8‐fold increase in flame propagation (128 mm s −1 ) driven by anisotropic thermal conduction and fluorine‐mediated interface activation. This work establishes geometric‐interfacial nanoarchitectonics as a paradigm to synchronize stress, charge, and heat transport, enabling next‐generation energetic materials for aerospace and Micro‐Electromechanical Systems (MEMS).