Abstract Progress in commercializing solid polymer electrolytes (SPEs) for lithium metal batteries (LMBs) has been impeded by challenges, like concentration polarization, non‐uniform Li + flux, and an unstable solid electrolyte interface (SEI), which contribute to dendrite formation. To address these issues, silica framework (SF)‐based single‐ion conductors are proposed, featuring a unique solvation channel composed of a fluorinated segment, a high‐dipole zwitterion, and a rotation‐motion‐driven ion‐hopping medium. This design promotes low resistance at the cathode/electrode interface, suppresses dendrite growth at the anode/electrolyte interface, and maintains a uniform Li + flux. This results show that continuous ion channels within a robust framework enhance Li‐ion dissociation and transport, achieving high ionic conductivity (σ DC = 8.8 × 10 −4 S cm −1 ), a modulus of 0.9 GPa, a high lithium transference number (≈0.83), and an extended electrochemical stability window (up to 5.2 V) at 25 °C. This design fosters the formation of a hybrid organic/inorganic SEI layer composed of Li 2 CO 3 , LiF, and Li 2 O, enabling ultra‐stable Li plating/stripping for over 4000 h at 0.1 mA cm −2 . Furthermore, the full cells demonstrate excellent rate performance and long‐term cycling stability and capacity retention (81% for Li||LFP and 86% for Li||NCM811 after 400 cycles at 1 C) and high coulombic efficiency, offering a promising strategy to stable LMBs.