Hierarchical 3D sisal-like CuO/ZnO nanostructures assembled from nanorods have been successfully synthesized by a facial one-step solution with a chelating agent 1,2-ethylenediamine (EDA). XRD patterns have revealed that the prepared sisal-like nanostructures show single-crystalline behavior. The concentration of NaOH has strong influence on sisal-like nanostructures. Moreover, formation mechanism of CuO/ZnO 3D sisal-like nanostructures was proposed. The hierarchical CuO/ZnO exhibited high catalytic performance on thermal decomposition of Ammonium perchlorate (AP) determined by TG and DSC.