This paper presents the combustion characteristics of various copper oxide (CuO) nanorods/aluminum (Al) nanothermite compositions and hybrid nanoenergetic mixtures formed by combining nanothermites with either ammonium nitrate (NH4NO3) or secondary explosives such as RDX and CL-20 in different weight proportions. The different types of nanorods prepared in this study are referred to as CuO-VD (dried under vacuum at 25 degrees C for 24 h), CuO-100 (at 100 degrees C for 16 h) and CuO-400 (short time (1 min) calcination at 400 degrees C). The physical and chemical characteristics of these different kinds of CuO nanorods were determined using a variety of analytical tools such as X-ray diffractometer, transmission electron microscope (TEM). Fourier transform infrared spectrometer (MR), surface area analyzer and simultaneous differential scanning calorimeter (DSC)/thermogravimetric analyzer (TGA). These measured characteristics were correlated with the combustion behavior of the nanoenergetic compositions synthesized in this work. The use of different drying and calcination parameters produced the synthesis of CuO nanorods with varying amount of hydroxyl (OH) and CHn (n = 2, 3) functional groups. The experimental observations confirm that the presence of these functional groups on the surface of CuO nanorods enabled the formation of assembled nanoenergetic composite, upon mixed with Al nanoparticles. A facile one-step synthesis of assembled composite through surface functionalization is reported and it can be extended to large-scale preparation of assembled nanoenergetic mixtures. The combustion behavior was studied by measuring both combustion wave speed and pressure-time characteristics. Pressurization rate was determined by monitoring the pressure-time characteristics during the combustion reaction initiated by a hot wire in a fully-confined geometry. Different amounts of nanothermite powder were packed in the same volume of combustion chamber by applying different packing pressures and the pressure-time characteristics were measured as a function of varying percent theoretical maximum density (% TMD). The experimental setup used in this work enabled us to study the functional behavior of initiating explosives such as NH4NO3 nanoparticles, RDX and CL-20 using nanothermites under fully-confined test geometry. The dent tests performed on lead witness plates support the experimental observations obtained from pressure-time and combustion wave speed measurements of hybrid mixtures. (C) 2011 The Combustion Institute. Published by Elsevier Inc. All rights reserved.