The　practical　application　of　Zn-ion　batteries　(ZIBs)　faces　several　challenges,　particularly　regarding　poor　reversibility　and　the　reactivity　of　water　in　the　electrolytes　across　a　wide　temperature　range.　Herein,　this　study　presents　the　design　of　a　ternary　electrolyte　with　significant　intermolecular　interactions　based　on　tetrahydrofurfuryl　alcohol　(THFA),　H2O,　and　Zn(OTf)2　to　address　these　challenges　from　−40　to　60　°C.　The　ether　alcohol　compound　THFA　effectively　mitigates　the　side　reactions　about　water,　by　disrupting　and　suppressing　the　reactivity　of　the　dominant　water-based　clusters.　Through　experimental　and　theoretical　investigations,　the　structural　and　mechanistic　insights　of　ternary　solvation　clusters　are　uncovered.　The　hydrogen-bond-induced　interactions　of　THFA　facilitate　the　participation　of　OTf−　in　solvation　clusters　and　bidentate　chelation　coordination　with　Zn2+　ensures　the　formation　of　lean-water　solvation　clusters.　Furthermore,　the　interfacial　electrochemistry　on　the　Zn　surface　is　also　regulated　to　exhibit　a　preferential　layer-by-layer　(0　0　2)　oriented　deposition　with　a　stable　solid　electrolyte　interface　(SEI).　As　a　result,　The　Zn||VO2　battery　using　ternary　electrolyte　maintains　a　capacity　of　237.5　mAh　g−1　with　an　86.71%　retention　after　500　cycles　at　60　°C　and　3　A　g−1,　while　it　exhibits　stable　cycle　even　at　−40　°C　over　200　cycles　with　almost　no　capacity　decrease.　©　2023　Wiley-VCH　GmbH.