To enhance the catalytic effect of nano-sized metals for the thermal decomposition of ammonium perchlorate (AP), Ni@C nanorods were prepared by combining solvothermal method and high-temperature calcining process using nickel-based metal-organic frameworks (Ni-MOFs) as precursor. The morphology, structure and composition of Ni@C nanorods were characterized by X-ray diffractometer (XRD), field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectrometer (XPS), Raman spectrometer, full-automatic physical adsorption analyzer and so on. The catalytic effect of Ni@C nanorods on the thermal decomposition of AP at different calcination temperatures was studied by differential scanning calorimeter (DSC). Results show that Ni@C nanorods are porous core-shell structures with metal Ni as core and graphitized C layer as shell, and highly graphitized C layer effectively prevents the oxidation of nano-Ni particles. Ni@C nanorods possess more superior catalytic performances on the thermal decomposition of AP than single Ni nanoparticles and C nanorods. In particular, Ni@C nanorods calcined at 1000 ℃ make the peak temperature of high-temperature decomposition of AP reduce from 423.4 ℃ to 323.8 ℃, the apparent heat of decomposition increase from 825.4 J·g^-1 to 1423.8 J·g^-1, and the activation energy of reaction decrease from 172.50 kJ·mol^-1 to 130.04 kJ·mol^-1.