4,4′-Bis-1,2,4-triazole (2, BTr) was synthesized from N,N-dimethylformamide azine dihyfrrochloride (1) and 4-amino-1,2,4-triazole in toluene as solvent. The structure of BTr was characterized by ¹H NMR, IR, MS and element analysis. The single crystal of BTr was also cultivated successfully and determined by a X-ray single crystal diffractometer. The effect of reaction solvent, molar ratio, time and temperature on the yield of BTr were investigated. Results show that using toluene as reaction slovent, the optimal conditions of preparation are as follow: molar ratio of 1 to 4-amino-1,2,4-triazole 1:1.2, time 8 h, temperature 110 ℃, the yield is 86.4%. And the crystal of title compound is orthorhombic system, space group Pnma with crystal parameters of a=0.69712(14) nm, b=0.74045(15) nm, c=1.1156(2) nm, V=0.5759(2) nm³, Z=4, D_c=1.570 g·cm^-3, F(000)=280, R₁=0.043, ωR₂=0.1222. The two triazole rings in BTr are vertical to each other, and that should be beneficial to the stability of the molecule due to the least steric hindrance..