AbstractThe compositions and microstructures, thermolyses, and sensitivities of 3,3‐bis(azidomethyl)oxetane (BAMO) copolymers with 3‐nitratomethyl‐3‐methyloxetane (NMMO) were characterized. The molar ratios of monomers fed in the copolymerizations were: BAMO/NMMO = 8/2, 7/3, and 6/4. The observed compositions were 81/19, 68/32, and 60/40, respectively. The relative compositions of trade microstructures were also exactly the same as theoretical values. The copolymerization of BAMO with NMMO behaved like an ideal system in the sense that the copolymer has approximately the same composition as the monomer fed. The microstructures of copolymers were also randomly arranged. Poly BAMO showed side chain decomposition in the initial stage of the thermolysis, on the other hand, backbone decomposition controlled the thermolysis of poly NMMO. The BAMO units and the NMMO units appeared to decompose more or less independently of one another and retained their individual decomposition characteristics despite being copolymerized. However, the heat generated by the NMMO decomposition, which occurred at 40°C lower than that of BAMO. activated the reaction of BAMO. Poly B/N(7/3) showed very interesting characteristics in sensitivities, mechanical properties, and the heat of decomposition.