A thermoplastic fluorescent polyurethane was prepared by using polycarbonate diol (PCDL) and hexamethylene diisocyanate (HDI) as main raw materials, 1,4-butanediol (BDO) and fluorescent molecule diol N, N-dihydroxyl phenylaniline-β-terpyridine (TPPDA) as a chain extender. And the fluorescent polymer electrolyte was prepared by blending thermoplastic fluorescent polyurethane with lithium difluoromethane sulfonimide (LiTFSI). The structure, optical properties, mechanical properties, thermal stability and electrochemical properties of the prepared electrolyte were tested using a Fourier transform infrared spectrometer, a fluorescence spectrometer, a tensile tester, a synchronous thermal analyzer, an electrochemical workstation, and a battery tester. Studies have shown that as the mass fraction of lithium ion (LiTFSI) in the film increases, the fluorescence intensity increases; when the mass fraction of lithium salt is 30%, the tensile strength reaches 4.5 MPa, and the conductivity reaches 1.03?10-4 S/cm. The half-cell assembled with a fluorescent polyurethane electrolyte membrane with a lithium salt mass fraction of 30% did not undergo significant oxidative decomposition within 2 to 4.5 V, and the full battery of the specific discharge capacity reached 165 mA?h/g and 111 mA?h/g at 0.2 C and 1 C current density respectively at 80℃ and it exhibited good rate performance.