Reactive metal/metal-oxide based nanoenergetic materials find tremendous applications in propellants, explosives, and pyrotechnics. This paper reports on the synthesis of CuO nanobricks (CuOnb) using simple and rapid solid-state methods and investigation of the combustion reactivity (combustion propagation speed, peak pressure and pressurization rate) of as-synthesized copper oxide nanobricks with nano-aluminum and catalytic activity of copper oxide nanobricks in thermal decomposition of lithium perchlorate (LiClO4). The X-ray diffractometry (XRD) and transmission electron microscopy revealed the fabrication of CuO nanobricks (length of sub-150 nm with square cross-section of size of sub-25 nm). The CuOnb based nano-aluminum energetic composites (Al/CuOnb) exhibited excellent combustion characteristics with combustion propagation speed of 1,760 ± 25 m/s, peak pressure of 61.2 MPa, pressurization rate of 1.02 MPa/µs and heat of reaction of 750 J/g respectively. The copper oxide nanobricks expressed high catalytic activity in thermal decomposition of LiClO4 by accelerating the thermal decomposition to start and accomplish at lower temperature than the pure lithium perchlorate. © 2020 Taylor & Francis Group, LLC.