Three-dimensional CoFe2O4 superstructures are prepared by the controlled thermal decomposition of the complex oxalate with various hierarchical nanostructures, which are obtained via poval (PVA) mediated precipitation reaction. The influence of experimental parameters including the concentration of PVA, reaction temperature, and reaction time was systematically investigated to study the possible formation mechanism of the superstructure. The as-prepared samples are characterized by X-ray powder diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, and high-resolution transmission electron microscopy. The catalytic property of the as-prepared superstructure is also carried out. The results show that the hierarchical structure presents superior catalytic activity for ammonium perchlorate by decreasing its decomposition temperature to as low as 290 degrees C and more decomposition occurs at the low temperature phase (LTD) stage. (C) 2014 Elsevier B.V. All rights reserved.