To solve the problems of igniting difficulty and combustion agglomeration， modification of Al powder by alloying and oxidant coating was studied. AP@Al/Ni composite fuels were prepared by acoustic resonance mixing technique. The heats of reaction of the composite fuels with different ammonium perchlorate （AP） contents were measured using a bomb calorimeter. The morphology characteristics of the optimized AP@Al/Ni composite fuel were analyzed by SEM. The thermal reactivity of AP， Al/AP mixture， Ni/AP mixture， and AP@Al/Ni composite fuel were comparatively studied by DSC/TG. The effects of additives including Al， Ni， and Al/Ni composite on the thermal decomposition kinetic parameters of AP were evaluated by the non-isothermal kinetic method. The results show that the heat of reaction of the composite fuel reaches its maximum when the mass content of AP is 38.90%， which is considered as the optimal content of AP in the formula. Compared with Al and Ni， the Al/Ni composite has the most significant influence on the thermal decomposition of AP， which reduces the peak temperature of AP in high temperature decomposition by 76.9 ℃ and increases the heat release by 84.8%. The apparent activation energy of AP decomposition in AP@Al/Ni composite fuel that obtained by Friedman method is 103.9 kJ·mol^-1， and this process obeys the three-dimensional random nucleation and nucleus growth （A3） model.