A novel green initiating explosive-dipotassium 5, 5′-bis(tetrazole-1-oxide)(BTOK) was synthesized using 1H, 1′H-5, 5′-bistetrazole-1, 1′-diolate(BTO) as starting material. The single crystal of target compound was cultivated by the slow evaporation method, and its crystal structure was determined by X-ray single crystal diffraction. The thermal decomposition behavior of BTOK was investigated through DSC and TG-DTG technologies. Its 5 s explode temperature, impact sensitivity, friction sensitivity and 50% fire energy were measured. Results show that the K⁺ and BTO^2- form a dissymmetrical structure; in different layers, they are alternately arranged and connected with each other, forming a three-dimensional network structure. BTOK has a good thermal stability with a decomposition temperature beginning at 307 ℃ and its exothermic process has obvious primary explosive characteristics. For BTOK, the 5 s explosive temperature is 321 ℃, the friction sensitivity of BTOK is 56%, under the condition of 70°, 1.23 MPa, the impact sensitivity (H₅₀) is 22.5 cm, with the drop hammer of 800 g and the 50% fire energy of electrostatic spark sensitivity is 0.21 J.