Zinc-ion　batteries　(ZIBs)　have　promising　prospects　in　energy　storage　field,　but　the　water　molecules　in　aqueous　electrolytes　significantly　compromise　the　stability　of　the　anode　and　cathode　interfaces　and　hinder　the　low-temperature　performance.　Herein,　water-in-oil　type　Möbius　polarity　topological　solvation　composed　of　oil,　water,　and　amphiphilic　salt　are　first-ever　pioneered,　forming　the　surfactant-free　microemulsion　electrolyte　(SFMEE).　This　water-in-oil　type　Möbius　solvation　structure,　characterized　by　its　distinct　inner　and　outer　layers　and　a　polarity　inversion　feature,　successfully　connects　the　non-polar　phase　with　the　polar　phase,　eliminating　the　need　for　surfactants　to　reduce　costs　and　system　complexity.　The　amphiphilic　anion　of　salt　creates　a　polarity　singularity　and　stabilizes　the　polarity-reversed　encapsulation.　The　outer　oil　layer　disrupts　the　cohesive　polarity　network　of　water　and　constructs　a　polarity-reversed　cage　to　restrict　water.　A　series　of　SFMEE　combinations　are　investigated　and　then　directly　applied　to　ZIBs,　confirming　excellent　universality　and　durability　of　this　design.　The　Zn||NVO　(NaV₃O₈·1.5H₂O)　cells　using　SFMEE　can　stably　cycle　for　4000　cycles　with　a　capacity　of　125　mAh　g−1　and　86.8%　capacity　retention.　This　discovery　of　Möbius　solvation　structure　unlock　unprecedented　levels　of　electrolyte　design　and　illuminate　the　development　of　next-generation　high-performance　energy　storage　systems.　©　2025　Wiley-VCH　GmbH.