This article introduces a molecular anchoring approach to improve the performance and safety of lithium metal batteries by restricting the reactivity of free ether solvents in diluted electrolytes. Traditional high-concentration electrolytes face challenges such as severe side reactions and exothermic reactions with lithium metal under high voltages. The proposed molecular anchoring method uses hydrogen-bonding interactions to suppress excessive ether side reactions, enhancing the stability of nickel-rich cathodes at 4.7 V. This approach also mitigates exothermic processes under thermal abuse conditions, delaying battery thermal runaway. The study highlights the advantages of this method over conventional high-concentration electrolytes, including better oxidation stability, improved Coulombic efficiency, and enhanced safety. The research demonstrates the potential of molecular anchoring in developing high-voltage and high-safety lithium metal batteries.This article introduces a molecular anchoring approach to improve the performance and safety of lithium metal batteries by restricting the reactivity of free ether solvents in diluted electrolytes. Traditional high-concentration electrolytes face challenges such as severe side reactions and exothermic reactions with lithium metal under high voltages. The proposed molecular anchoring method uses hydrogen-bonding interactions to suppress excessive ether side reactions, enhancing the stability of nickel-rich cathodes at 4.7 V. This approach also mitigates exothermic processes under thermal abuse conditions, delaying battery thermal runaway. The study highlights the advantages of this method over conventional high-concentration electrolytes, including better oxidation stability, improved Coulombic efficiency, and enhanced safety. The research demonstrates the potential of molecular anchoring in developing high-voltage and high-safety lithium metal batteries.