The energy release performance of energetic compounds like 3-nitro-1,2,4-trizole-5-one (NTO) and 5,5'-bistetrazole-1,1'-diolate (TKX-50) are indispensable in propellent formulations. However, thermal decomposition behavior is impeded by unfavorable catalysts. Presently, ultrathin porous MoS2 nanosheets (pMoS2) are considered as high-performance catalysts for NTO and TKX-50 decomposition. The pMoS2 in 5 wt% content could decrease the decomposition temperature of NTO and TKX-50 by 13.5 °C and 37.1 °C, respectively. Furthermore, the exothermic heat-release for pMoS2@NTO and pMoS2@TKX-50 were increased almost by a factor of two. The porous structure combined with large specific area of pMoS2 could mostly trigger the catalytic effect towards energetic compound decomposition. Additionally, the as-obtained MoS2 endowed advances in safety performance of NTO and TKX-50, with remarkably reduced impact and friction sensitivity. The as-proposed strategy may stimulate a different perspective towards the fast decomposition of energetic materials in propellants.