Nearly monodisperse CuO hollow microspheres were successfully synthesized by a straightforward one-pot hydrothermal approach using dicyandiamide (DDA) as structure-guiding agent. The composition, structure and morphology of the products were investigated in detail, via a set of characterizations including X-ray diffraction (XRD) pattern, energy dispersive X-ray (EDX), scanning electron microscope (SEM), and transmission electron microscope (TEM). The results demonstrated that different copper sources and experimental procedures would significantly affect the shape or size of CuO products. A possible formation mechanism of CuO microspheres in this process was thoroughly discussed. Also, some other novel CuO microstructures were fabricated based on DDA-mediated synthetic route. DSC/TGA analysis revealed that as-prepared CuO microspheres can be explored as a promising additive to accelerate the thermal decomposition of ammonium perchlorate. a key oxidizer in composite solid propellants. (c) 2009 Published by Elsevier B.V.