A novel entanglement association polymer electrolyte, PVFH-PVCA, has been developed for Li-metal batteries. This electrolyte is composed of a PVFH matrix and a PVCA stabilizer, which enhances mechanical properties and eliminates stress from dendrite growth. The PVCA stabilizer promotes the formation of a stable cathode–electrolyte interphase, leading to high specific capacity and excellent cycling stability. The PVFH-PVCA electrolyte enables Li//Li symmetric cells to cycle for over 4500 hours at 8 mA cm⁻². The electrolyte also supports high-performance full cells, such as Li₁.₂Mn₀.₅₆Ni₀.₁₆Co₀.₀₈O₂/PVFH-PVCA/Li, which achieved 125 cycles at 1 C with a stable discharge capacity of ~2.5 mAh cm⁻². The electrolyte's high ionic conductivity (2.04 × 10⁻³ S cm⁻¹) and strong antioxidant potential, along with its robust polar groups, improve mechanical properties and enable a tensile strength of 19.83 MPa. The PVFH-PVCA electrolyte exhibits excellent compatibility with various cathode materials, including LiCoO₂, LiFePO₄, and LiNi₀.₉₅Co₀.₀₅O₂, demonstrating its universal applicability. The electrolyte's entangled structure enhances interfacial stability, suppresses dendrite growth, and improves cycle life. The PVFH-PVCA electrolyte also enables high-loading Li||LMNCO pouch batteries with outstanding cycling performance and high surface capacity. This study provides a new approach for high-energy-density Li–LRMO batteries.A novel entanglement association polymer electrolyte, PVFH-PVCA, has been developed for Li-metal batteries. This electrolyte is composed of a PVFH matrix and a PVCA stabilizer, which enhances mechanical properties and eliminates stress from dendrite growth. The PVCA stabilizer promotes the formation of a stable cathode–electrolyte interphase, leading to high specific capacity and excellent cycling stability. The PVFH-PVCA electrolyte enables Li//Li symmetric cells to cycle for over 4500 hours at 8 mA cm⁻². The electrolyte also supports high-performance full cells, such as Li₁.₂Mn₀.₅₆Ni₀.₁₆Co₀.₀₈O₂/PVFH-PVCA/Li, which achieved 125 cycles at 1 C with a stable discharge capacity of ~2.5 mAh cm⁻². The electrolyte's high ionic conductivity (2.04 × 10⁻³ S cm⁻¹) and strong antioxidant potential, along with its robust polar groups, improve mechanical properties and enable a tensile strength of 19.83 MPa. The PVFH-PVCA electrolyte exhibits excellent compatibility with various cathode materials, including LiCoO₂, LiFePO₄, and LiNi₀.₉₅Co₀.₀₅O₂, demonstrating its universal applicability. The electrolyte's entangled structure enhances interfacial stability, suppresses dendrite growth, and improves cycle life. The PVFH-PVCA electrolyte also enables high-loading Li||LMNCO pouch batteries with outstanding cycling performance and high surface capacity. This study provides a new approach for high-energy-density Li–LRMO batteries.