Lithium　metal　batteries　(LMBs)　are　promising　for　next-generation　high-energy-density　batteries　owing　to　the　highest　specific　capacity　and　the　lowest　potential　of　Li　metal　anode.　However,　the　LMBs　are　normally　confronted　with　drastic　capacity　fading　under　extremely　cold　conditions　mainly　due　to　the　freezing　issue　and　sluggish　Li+　desolvation　process　in　commercial　ethylene　carbonate　(EC)-based　electrolyte　at　ultra-low　temperature　(e.g.,　below　-30　degrees　C).　To　overcome　the　above　challenges,　an　anti-freezing　carboxylic　ester　of　methyl　propionate　(MP)-based　electrolyte　with　weak　Li+　coordination　and　low-freezing　temperature　(below　-60　degrees　C)　is　designed,　and　the　corresponding　LiNi0.8Co0.1Mn0.1O2　(NCM811)　cathode　exhibits　a　higher　discharge　capacity　of　84.2　mAh　g(-1)　and　energy　density　of　195.0　Wh　kg(cathode)(-1)　than　that　of　the　cathode　(1.6　mAh　g(-1)　and　3.9　Wh　kg(cathode)(-1))　working　in　commercial　EC-based　electrolytes　for　NCM811||　Li　cell　at　-60　degrees　C.　Molecular　dynamics　simulation,　Raman　spectra,　and　nuclear　magnetic　resonance　characterizations　reveal　that　rich　mobile　Li+　and　the　unique　solvation　structure　with　weak　Li+　coordination　are　achieved　in　MP-based　electrolyte,　which　collectively　facilitate　the　Li+　transference　process　at　low　temperature.　This　work　provides　fundamental　insights　into　low-temperature　electrolytes　by　regulating　solvation　structure,　and　offers　the　basic　guidelines　for　the　design　of　low-temperature　electrolytes　for　LMBs.