Poly (ethylene oxide) (PEO)-based polymer electrolytes have promising applications in all-solid-state lithium metal batteries. However, their wide range of practical applications is severely limited by their relatively low room temperature lithium ion conductivity and narrow electrochemical window. In this paper, based on the ability of spontaneous polarization of ferroelectric materials to generate polarization field under applied electric field and the characteristics of Metal-Organic-Frameworks (MOFs) materials with regular adjustable pore structure, a Nano material combining ferroelectric materials and MOF (NUS-6(Hf)-MOF) was first proposed to be added to PEO polymer electrolyte as a filler. NUS-6(Hf)-MOF can provide rapid transport channel for lithium ion, born under the applied electric field of the latter's consistent dipole polarization field can adjust the interface of the space charge distribution, the composite polymer electrolyte (NUSCPE) modified with NUS-6(Hf)-MOF has high ionic conductivity (1.16 × 10