This work reported on the thermal decomposition of ammonium perchlorate activated by addition of NiO nanocrystals with different surface areas. NiO samples were characterized by X-ray diffraction (XRD), transition electron microscope (TEM), Brunauer-Emmett-Teller (BET) technique, Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy. With increasing annealing temperature, the surface areas of NiO samples reduced from 108.6 to 0.9 m2 g−1. The catalytic activities of NiO nanocrystals on the thermal decomposition of ammonium perchlorate were investigated by thermogravimetric analysis (TG) coupled with differential thermal analysis (DTA). With addition of NiO nanocrystals, thermal decomposition temperature of AP decreased greatly. Larger surface areas of NiO nanocrystals promoted the thermal decomposition of AP.