High energy density and rapid reactivity are the future trend for nano-energetic materials. Energetic performance of nano-energetic materials depends on the interfacial diffusion and mass transfer during the reacted process. However, the development of desired structure to significantly enhance reactivity still remains challenging. Here we focused on the design and preparation of 3D porous hollow Co3O4 micro-spheres, in which gas-blowing agents (air) and maximize interfacial interactions were introduced to enhance mass transport and reduce the diffusion distance between the oxidizer and fuel (Aluminum). The 3D hierarchical Co3O4/Al based nano-energetic materials show a low-onset decomposition temperature (423 degrees C), and high heat output (3118 J g(-1)) resulting from porous and hollow nano-structure of Co3O4 micro-spheres. Furthermore, 3D hierarchical Co3O4/Al arrays were directly fabricated on the silicon substrate, which was fully compatible with silicon-based microelectromechanical systems to achieve functional nanoenergetics-on-a-chip. This approach provides a simple and efficient way to fabricate 3D ordered nano-energetic arrays with superior reactivity and the potential on the application in micro-energetic devices. (C) 2018 Elsevier B.V. All rights reserved.