The regulation of hydrogen-bonding networks in molecular switches is critical for adaptive materials. However, most of the reported molecular switches are not capable of modulating hydrogen-bonding networks in energetic materials, limiting high-demand applications in explosives. In this work, the first high-energy nitroamino-based molecular switch is reported. It can control the complex hydrogen-bonding systems of energetic materials by reversible cycling for property modulation. Through alkali-acid stimulation, the nitroamino-based switch undergoes dynamic transitions, which reconfigure H-bond networks and separate twin crystals (in x-ray verification). Supported by crystallography and theoretical modeling (e.g., the density of states), this switching mechanism modulates molecular planarity (Δθ >
60°) and optimizes the energy-stability balance, obtaining a compound 6-β with comprehensive properties comparable to classical explosives (e.g., RDX and HMX). By linking hydrogen-bonding engineering and energetic materials science through the nitroamino-based molecular switch, it facilitates superior energetic compounds that can be applied to defense equipment. In addition, our work establishes the nitroamino-based switch as a generalized tool for molecular engineering, bridging dynamic hydrogen-bonding control and self-assembly materials design.