A systematic investigation of the effects of different copper catalysts on the thermal behavior for ammonium dinitramide (ADN) was performed. ADN/copper catalyst mixtures were prepared in the ratio of 100/5 by grinding, and all samples were subjected to TG-DSC studies using thermo-gravimetric analysis coupled to Fourier Transformed Infrared Spectrometry (TGA-FTIR) and Mass Spectrometry, which obtained the detailed information of evolved gas products on pyrolysis and oxidative degradations. Four copper-series catalysts including copper chromate (CuCrO4), copper chromite (Cu2Cr2O5), copper 2,4-dihydroxybenzoate (beta-Cu) and metal-organic framework copper (MOF-Cu) were employed to research the appearance morphology and thermal behavior of the samples. TG-DSC analysis of the decomposition for ADN/catalyst revealed that copper chromite and beta-Cu exhibit higher catalytic activity than copper chromate due to their greater acceleration of thermal decomposition for ADN. Besides, though MOF-Cu slightly promote the thermal decomposition of ADN, the ADN/MOF-Cu system release more heat during exothermic reaction owing to the high energy of MOF-Cu.