AbstractIn order to improve of mechanical properties at low temperature region, 3,3‐bis(azidomethyl)oxetan (BAMO), 3‐nitratomethyl‐3‐methyloxetane (NMMO) and polyester (PE) copolymer were synthesized by using polyester initiator with boron trifluoride etherate. The molar ratio of each units in the BAMO/NMMO/PE copolymer was 7.4/2.6/0.39 according to the 1H‐NMR spectrum analysis and was almost exactly the same composition as the monomer fed (7/3/0.33). The relative composition of triad microstructures was same as theoretical value and they were randomly arranged. The PE, which was a replacement of 1,4‐butanediol, acted as an excellent soft segment in the copolymer, and the glass transition point of the elastomer was 4.8 degrees lowered by the replacement. This effect was also verified in the mechanical properties of the composite propellant and the tensile elongation was increased from 15% to 40%percnt; at −40 °C.