High-energy-density materials (HEDMs) require new design rules collected from experimental and theoretical results and a proposed mechanism. One of the targeted systems is the nitrogen-rich compounds as precursors for possible polymeric nitrogen or its counterpart in a reasonable pressure range. 1H-tetrazole (CH 2 N 4 ) with hydrogen bonds was studied under pressure by both diffraction and spectroscopy techniques. The observed crystal structure phase transition and hydrogen bond-assisted electronic structure anomaly were confirmed by first-principles calculation. The rearrangement of the hydrogen bonds under pressure elucidates the bonding interactions of the nitrogen-rich system in local 3D chemical environments, allowing the discovery and design of a feasible materials system to make new-generation high-energy materials.