Carbon nanotubes (CNTs) array confined with nano copper was prepared by electrochemical deposition method with CNTs array as working electrode. The effect of electrodeposition parameters on deposition of copper nanoparticle filled on CNTs array was studied. CNTs array confined with copper azide was obtained by gas-solid in-situ reaction. Scanning electron microscope, X ray diffracmeter and differential scanning calorimetry were used to characterize the structures and thermal properties of CNTs array confined with copper azide and nano copper. Results show that CNTs array confined with nano copper can be obtained at 1 mA and 10 mA. CNTs is not react wiht HN₃ during the in-situ process. CNTs array confined with copper azide can be initiated by thermal stimulus reliably. The 50% fire energy by Langlie method is 3.09 mJ.