The crystal structure of the solvate formed by explosive and solvent is very unstable, and it is easy to transfer to explosive crystal with the removal of the solvent molecules under certain conditions.To investigate the changes of microstructure and properties of hexanitrostilbene(HNS)/1, 4-dioxane(Dioxane) solvate in the process of rapid desolvation, the desolvation way of in-situ pyrolysis to sovent by in-situ X-ray powder diffraction(XRD) made the solvate decompose and a preliminary study of the micro-structure change and macro performance were performed.Results show that the desolvation of HNS/Dioxane solvate can be realized by in-situ XRD technique and the obtained HNS has microcrystal cluster and fine porous structure.Compared with conventional HNS, the surface area of desolvated HNS significantly increases from 1.6 m²·g^-1(raw HNS) to 3.7 m²·g^-1.The value of characteristic drop height H₅₀ of impact sensitivity decreases from 109.3 cm for raw HNS to 28.9 cm for desolvated HNS, and the value of energy required for initiation E₅₀ of electrostatic spark sensitivity decreases from 0.896 J for raw HNS to 0.413 J for desolvated HNS.The value of explosion probability point P of friction sensitivity decreases from 36% for raw HNS to 12% for desolvated HNS, revealing that the fast desolvation method of explosive of the solvate not only can obtain micro/nano porous HNS but also can effectively improve the response to different stimuli.