A facile chemical procedure capable of aligning CuO nanoparticles on graphene oxide (GO) in a water-isopropanol system has been described. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations indicate that the exfoliated GO sheets are decorated randomly by spindly or spherical CuO nanoparticle aggregates, forming well-ordered CuO:GO nanocomposites. A formation mechanism of these interesting nanocomposites is proposed as intercalation and adsorption of Cu2+ ions onto the GO sheets, followed by the nucleation and growth of the CuO crystallites, which in return resulted in the exfoliation of GO sheets. Moreover, the obtained nanocomposites exhibit a high catalytic activity for the thermal decomposition of ammonium perchlorate (AP), due to the concerted effect of CuO and GO.