The employment of TMOs as catalyst has been widely popularized in thermal decomposition and combustion process, especially in propellants and explosives application areas. The focus of this study is on investigating catalytic effects of Fe2O3, CuO, and NiO nanoparticles on thermal decomposition mechanism and kinetics behavior of 5-Amino-1H-Tetrazole (5AT), one typical energetic material. Experimental result reveals that thermal decomposition process of 5AT can be simplified from three steps to two steps with the additions of above TMOs. Thermal decomposition mechanisms of 5AT with and without TMOs are deduced by TG-FTIR-MS analysis. Results indicate that the interaction between TMOs and dissociation products shows the catalytic effect together with the variation of production phase. Both model-free and model-fitting methods are employed to evaluate thermal kinetics of catalyzed 5AT. During low temperature reaction range (below 300 degrees C), no obvious change is observed in activation energies or mastering reaction models (F-3 model). Conversely, catalytic effect of TMO is discovered mainly during high temperature range (above 300 degrees C), particularly during the polyaddition reaction of N-containing heterocycle and the ring-opening reaction of melem. The results of this study suggests that introducing TMOs nanostructure as catalysts into 5AT is a promising way to accelerate its combustion process in gas generation and propellant areas.