The　resurgence　of　lithium　metal　batteries　(LMBs)　has　opened　new　avenues　for　the　advancement　of　high-energy　density　secondary　batteries.　However,　the　electrochemical　performance　of　LMBs　at　extreme　temperatures　remains　suboptimal.　As　a　critical　component,　electrolytes　significantly　influence　the　wide-temperature　performance　of　LMBs.　Designing　an　electrolyte　system　with　superior　characteristics　represents　a　straightforward　and　effective　approach　to　expanding　the　operational　temperature　range　of　LMBs.　Here,　based　on　a　molecular　structure　design　perspective,　ethylene　glycol　dibutyl　ether　(EG)　was　selected　as　the　solvent　from　a　series　of　linear　ethers　to　develop　a　novel　localized　high-concentration　electrolyte　(EG-LHCE).　As　a　result,　the　substantial　steric　effect　induced　by　butyl　groups　in　EG　molecules　facilitates　the　formation　of　an　anion-rich　solvation　structure.　Furthermore,　the　diluent　not　only　further　promotes　the　rapid　de-solvation　of　Li+　through　dipole–dipole　interactions　with　EG,　but　also　co-decomposed　with　anions　to　establish　an　inorganic-rich　electrode/electrolyte　interface　(EEI).　Consequently,　4.4　V-class　Li||NCM811　cells　utilizing　EG-LHCE　exhibit　remarkable　stability　from　−30　to　60　℃.　Even　under　the　harsh　conditions　of　ultrahigh　loading　cathode　(21.5　mg/cm2)　and　limited　lithium　reservoir　(N/P　=　2),　stable　operation　is　maintained　(93　%,　150　cycles).　This　work　provides　valuable　insight　into　designing　electrolytes　for　wide-temperature　LMBs.　©　2025