In order to avoid using highly unstable and sensitive monomer 3,3-bis-azidomethyl oxetane, poly(3,3-bis-azidomethyl oxetane) (PBAMO) was successfully synthesized via azidation of poly(3,3-bis-bromo oxetane) (PBBrMO) in the aprotic and polar solvent cyclohexanone in the presence of a catalyst. It was found that the azidation proceeded very fast and almost completed in 6 h when the reaction temperature was up to 115 degrees C. PBAMO was characterized by gel permeation chromatography (GPC), Fourier transform infrared spectrometry (FTIR), hydrogen nuclear magnetic resonance ((1)H NMR), and carbon nuclear magnetic resonance ((13)C NMR).