Graphene oxide/nickel oxide (GO/NiO) nanocomposite has been successfully synthesized through a one-step hydrothermal procedure. The GO/NiO nanocomposite is characterized by Fourier transform infrared, X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray analysis. The influence of GO/NiO nanocomposites on the thermal decomposition of ammonium perchlorate (AP) is investigated by thermogravimetry, and differential scanning calorimetry analysis. The results reveal two stages thermal decomposition of pure AP changed to a one-stage highly exothermic process at much lower temperatures in the presence of GO/NiO nanocomposites. The released heat of AP -1 -1 thermal decomposition is increased from 649 J g for pure AP (AP0) to 1259 and 2195 J.g , for AP:GO/NiO 97:3 (AP3) and 95:5 (AP5) mixtures, respectively. Furthermore, decomposition temperature of AP significantly has decreased from 419 °C (AP0) to 307 °C (AP3) and 287 °C (AP5). The kinetic parameters are calculated by Kissinger equation for thermal decomposition of AP0 and AP5. The catalytic activity of GO/NiO nanocomposite is revealed by pre-exponential factor and -3 -1 the calculated activation energy, also the decomposition rate constant is increased from 4.2 × 10 s at 419 °C (pure AP) to -2 -1 1.04 × 10 s at 287 °C (peak temperature of AP5 sample).