In this study, few-layered tungsten disulfide ([WS.sub.2]) was prepared using a liquid phase exfoliation (LPE) method, and its thermal catalytic effects on an important kind of energetic salts, dihydroxylammonium-5,5'-bistetrazole-1,1'-diolate (TKX- 50), were investigated. Few-layered [WS.sub.2] nanosheets were obtained successfully from LPE process. And the effects of the catalytic activity of the bulk and few-layered [WS.sub.2] on the thermal decomposition behavior of TKX-50 were studied by using synchronous thermal analysis (STA). Moreover, the thermal analysis data was analyzed furtherly by using the thermokinetic software AKTS. The results showed the [WS.sub.2] materials had an intrinsic thermal catalysis performance for TKX-50 thermal decomposition. With the few-layered [WS.sub.2] added, the initial decomposition temperature and activation energy ([E.sub.a]) of TKX-50 had been decreased more efficiently. A possible thermal catalysis decomposition mechanism was proposed based on [WS.sub.2]. Two dimensional-layered semiconductor [WS.sub.2] materials under thermal excitation can promote the primary decomposition of TKX-50 by enhancing the H-transfer progress.