Biomimetic structures often endow materials with excellent performance. In order to explore the impact of biomimetic structures on the performance of energetic materials, the sedum multiceps-like bionic structure dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50) was constructed by self-assembly technology, and controllable particle size adjustment was achieved. Moreover, the effects of solvent ratio, solute content, stirring flow field, and temperature on the quality of sedum multiceps-like TKX-50 crystals were explored, and the formation mechanism of sedum multiceps-like TKX-50 crystals was analyzed. Then, the crystal morphology, crystal form and particle size distribution of sedum multiceps-like TKX-50 were characterized, furthermore, the thermal properties and mechanical sensitivity of sedum multiceps-like TKX-50 were emphatically studied. The results showed that the sedum multiceps-like biomimetic structure TKX-50 was assembled from needle shaped or sheet shaped small particle crystals, and the sedum multiceps-like structure did not change the explosive crystal form of TKX-50. What's more, the thermal decomposition activation energy of the prepared sedum multiceps-like TKX-50 crystal was at least 157.30 kJ⋅mol−1 and at most 185.27 kJ⋅mol−1, and the thermal energy was greatly affected by particle size. In addition, the minimum and maximum ultimate impact energy of the sedum multiceps-like TKX-50 crystals are 20 J and 55 J. The ultimate impact energy of the sedum multiceps-like TKX-50 crystal with different particle sizes is higher than that of the raw TKX-50 (15 J). As a consequence, the sedum multiceps-like bionic structure effectively improves the energy release of TKX-50, reduces the impact sensitivity, and improves the uniformity of particle size distribution.