The molecular structure of butadiene peroxide is unstable, which can generate a large amount of heat in decomposition reaction. When the rate of heat generation is higher than the rate of heat release, the heat balance of system is broken out, which will produce self-heat and initiate thermal explosion. This paper calculated the critical thermal explosion temperature of decomposition reaction of butadiene peroxide roughly on the basic of thermal explosion theory. The result showed that butadiene peroxide has very low critical thermal explosion temperature comparing with RDX and TNT. So it is very dangerous in thermal stability.