Molecular Polarization Engineering Homogenizes Interfacial Potential for Long‐Life Wide‐Temperature Solid‐State Lithium Metal Batteries

Lithium dendrite formation in solid‐state lithium metal batteries originates not only from mechanical failure but also from spatially heterogeneous interfacial electrostatic fields that induce localized Li + accumulation. However, existing electrolyte designs mainly regulate mechanical strength or chemical interfacial reactions, while dynamic regulation of interfacial electrostatic disorder remains unexplored. Here, we introduce an interfacial potential homogenization enabled by polarization‐mediated regulation. A molecularly entangled PEO/polyurethane/MOF‐177 electrolyte is constructed, where polar polymer networks and MOF polarization domains cooperatively redistribute local electric‐field fluctuations. This electrostatic regulation homogenizes Li + flux, lowers migration barriers, and suppresses preferential lithium nucleation. Consequently, CPEZ exhibits an ionic conductivity of 1.9 × 10 −3 S cm −1 and a Li + transference number of 0.71, both measured at 60°C. The Li/CPEZ/Li cell cycles stably for 9000 h at 0.1 mAh cm −2 . The Li/CPEZ/LFP retains 90 % capacity after 5000 at 1 C, while Li/CPEZ/LFP retains 85% capacity after 500 cycles at 100°C and cycles stably for 150 cycles at −15°C. This work establishes electrostatic regulation via polar interactions as a transferable design principle for durable, wide‐temperature solid‐state lithium metal batteries.