Catalytic activity of three kinds of Cu2O cubes with different structures for thermal decomposition of ammonium perchlorate (AP) has been investigated in this paper. Cu2O crystals in the form of cubic aggregate, mono-dispersed cube and {100} planes etched cube have been synthesized through a microwave-assisted solvothermal method by adjusting the composition of solvent. The decomposition of AP in the presence or absence of Cu2O cubes has been investigated non-isothermally through thermogravimetry and differential scanning calorimetry (DSC). The data obtained from DSC have been applied for the calculation and comparison of the kinetic parameters of AP decomposition process through a model-free approach. The obtained kinetic parameters have been used to predict the reaction rate and progress of AP with Cu2O cubes under isothermal conditions or at temperature mode corresponding to real climate changes.