Sodium 5, 5′-bistetrazole-1, 1′-diolate tetrahydrate (SBTD·4H₂O), a key intermediate for the synthesis of energetic salts based on 1, 1′-dihydryoxl-5, 5′-bistetrazole (BTD), was synthesized by one-pot using dichloroglyoxime as starting material, and was characterized by infrared spectrum (IR), elemental analysis (EA) and scanning electron microscopy (SEM). The crystal structure of SBTD·4H₂O was determined by X-ray diffraction and its thermal behavior was determined by differential scanning calorimetry (DSC)-thermogravimetric (TG) analysis. Additionally, the impact and friction sensitivity of SBTD·4H₂O were determined according to GJB772A-1997. Results show that SBTD·4H₂O belongs to triclinic space groups P-1 with the density of 1.761 g·cm^-3, and the cell parameters are as following: a=5.6440(11) Å, b=6.4476(17) Å, c=8.303(11) Å, α=100.131(5)°, β=96.789(3)°, γ=112.157(3)°, V=1, D_c=1.761 g·cm^-3, F(000)=146, μ(Mo K_α)=0.227 mm^-1. SBTD·4H₂O starts to loss the crystal water at 84.4 ℃ with the heating rate of 10 K·min^-1, and it begins to decompose at 368.8 ℃ with the peak decomposition temperature of 398.6 ℃, which demonstrates that SBTD·4H₂O has good thermal stability. H₅₀ of SBTD·4H₂O is greater than 100 cm and friction sensitivity is 0%, showing the title compound insensitive to impact and friction.