The graphene oxide (GO) was found to be able to stabilize organic molecules including energetic compounds. However, the inherent mechanisms of such stabilization effects are still not well-known. Herein, various transition metal complexes of triaminoguanidine nitrate (TAGN) using GO as a dopant have been prepared and evaluated. It has been shown that the presence of GO could great improve the thermal stability of the resulted TAG-based complexes. The physical models governing their thermolysis for their initial rate-limiting decomposition steps are obtained using the state-of-the-art evaluation methods. These physical models are further supported by analyses of the overall gaseous products. In addition, the reaction pathways are proposed to explain the stabilization mechanisms of GO. For instance, by interaction of GO, the release of N-2 from TAG-Ni was greatly postponed. There is a broad secondary peak at temperature of 378 degrees C due to decomposition of the nickel nitrides, as the primary thermolysis intermediates of TAG-Ni. The formation of cobalt nitrides plays a significant role on decomposition of TAG-Co and G-T-Co, which results in much less heat release and mass loss in comparison to TAG-Ni.