In this study, novel peanut shaped CuO hollow architectures have been synthesized on a large scale through a facile one-pot hydrothermal method in the presence of water-soluble biopolymer sodium carboxymethyl cellulose as crystal growth modifiers. The as-obtained samples were investigated by a set of characterizations including field emission scanning electron microscopes (FE-SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD) pattern. A possible formation mechanism of this kind of peanut shaped CuO hollow architectures has also been proposed. Furthermore, the catalytic properties of as-obtained samples were investigated. It was found that these as-obtained peanut shaped CuO hollow architectures have good abilities to accelerate the thermal decomposition of ammonium perchlorate, an important oxidizer in composite solid propellants.