The fluorine-containing 3-azidomethyl-3-Methyloxetane (PAMMO) based thermoplastic elastomers were developed using PAMMO and the poly[3, 3-bis(2, 2, 2-trifluoro-ethoxymethyl)oxetane] glycol (PBFMO)preparing from a cationic polymerization as the raw materials, toluene-2, 4-diisocyanate (TDI) as the coupling agent to enhance its comprehensive properties. The molecular structure, relative molecular mass and mechanical properties of thermoplastic elastomers were confirmed by FT-IR, NMR, GPC, DSC, TG/DTG and universal testing machine respectively. The results show that the number average relative molecular mass of the thermoplastic elastomers was 38200, the decomposition temperature(T_d) was found to be 220 ℃, the tensile strength at break was 15 MPa, and the corresponding elongation was 700%. Therefore, the thermoplastic elastomers exhibited good thermal stability and mechanical properties.