The currently used primary explosives, such as lead azide and lead styphnate, present serious health hazards due to the toxicity of lead. There is a need to replace them with equally energetic but safer-to-handle and more environmentally friendly materials. Copper azide is more environmentally acceptable, but very sensitive and detonates easily from electrostatic charges during handling. If the highly sensitive copper azide is encapsulated within conducting containers, such as anodic aluminum oxide (AAO)-templated carbon nanotubes (CNTs), its sensitivity can be tamed. This work describes a technique for confining energetic copper azide within CNTs. ∼5 nm colloidal copper oxide nanoparticles are synthesized and filled into the 200 nm diameter CNTs, produced by template synthesis. The Cu-O inside the CNTs is reduced in hydrogen to copper, and reacted with hydrazoic acid gas to produce copper azide. Upon initiation, the 60 μm long straight, open-ended CNTs guide decomposition gases along the tube channel without fracturing the nanotube walls. These novel materials have potential for applications as nano-detonators and green primary explosives; they also offer new opportunities for understanding the physics of detonation at the nanoscale.