Two hollow CuFe₂O₄ nanospheres (CuFe₂O₄-p and CuFe₂O₄-d) were successfully prepared using a hydrothermal method. CuFe₂O₄-p has a smaller size and higher BET specific surface area compared to CuFe₂O₄-d. The catalytic activity of nano-CuO, nano-Fe₂O₃, physically mixed CuO + Fe₂O₃, CuFe₂O₄-p, and CuFe₂O₄-d on the thermal decomposition of RDX and FOX-7 were comparatively investigated by differential scanning calorimetry (DSC) method. The results showed that CuFe₂O₄-p and CuFe₂O₄-d exhibited higher catalytic activity than the others, and the apparent activation energies of decomposition were reduced by 37.7 and 28.4 kJ mol⁻¹ for RDX, 40.1 and 30.5 kJ mol⁻¹ for FOX-7, respectively. The catalytic performance of CuFe₂O₄-p for the decomposition of RDX and FOX-7 was superior to that of CuFe₂O₄-d.