The study addresses the issue of lithium dendrite growth, a major challenge in achieving high-performance lithium metal batteries (LMBs). The researchers construct a lithium nitrate (LiNO₃)-implanted electroactive β phase polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) crystalline polymorph layer (PHL). The PHL layer, with its electronegatively charged polymer chains, forms lithium-ion charged channels on the surface, which act as reservoirs to sustainably release Li ions and reduce the ionic flux in the electrolyte. This approach not only decreases the growth of lithium dendrites but also accelerates Li ion transport. The PHL layer exhibits high ionic conductivity, enabling uniform Li deposition and high Coulombic efficiency (CE) of 97.0% over 250 cycles in a Li∥Cu cell. Additionally, the PHL-Cu@Li anode shows stable symmetric plating/stripping behavior over 2000 hours at 3 mA cm⁻² with an ultrahigh Li utilization of 50%. Full cells with PHL-Cu@Li anodes and LFP or NCM cathodes demonstrate long-term cycle stability, with high capacity retention rates of 95.9% and 84.3%, respectively, after 900 cycles and 100 cycles under harsh conditions. The study highlights the potential of LiNO₃ in ester-based electrolytes for practical high-voltage LMBs.The study addresses the issue of lithium dendrite growth, a major challenge in achieving high-performance lithium metal batteries (LMBs). The researchers construct a lithium nitrate (LiNO₃)-implanted electroactive β phase polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) crystalline polymorph layer (PHL). The PHL layer, with its electronegatively charged polymer chains, forms lithium-ion charged channels on the surface, which act as reservoirs to sustainably release Li ions and reduce the ionic flux in the electrolyte. This approach not only decreases the growth of lithium dendrites but also accelerates Li ion transport. The PHL layer exhibits high ionic conductivity, enabling uniform Li deposition and high Coulombic efficiency (CE) of 97.0% over 250 cycles in a Li∥Cu cell. Additionally, the PHL-Cu@Li anode shows stable symmetric plating/stripping behavior over 2000 hours at 3 mA cm⁻² with an ultrahigh Li utilization of 50%. Full cells with PHL-Cu@Li anodes and LFP or NCM cathodes demonstrate long-term cycle stability, with high capacity retention rates of 95.9% and 84.3%, respectively, after 900 cycles and 100 cycles under harsh conditions. The study highlights the potential of LiNO₃ in ester-based electrolytes for practical high-voltage LMBs.