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Here, we show that incorporating an ionic liquid modified ZIF\u201067 (IL@ZIF\u201067) into a polymer solid electrolyte enables deliberate reorganization of ion coordination and reconfiguration of Li\n                    <jats:sup>+<\/jats:sup>\n                    transport pathways at the molecular level. ZIF\u201067 sites preferentially anchor TFSI\n                    <jats:sup>\u2212<\/jats:sup>\n                    , while confined ionic liquid domains reshape Li\n                    <jats:sup>+<\/jats:sup>\n                    coordination, establishing a dynamic ion\u2010pair network with weakened Li\n                    <jats:sup>+<\/jats:sup>\n                    \u2010anion coupling and spatially restricted anions. This coordination reorganization decouples long\u2010range Li\n                    <jats:sup>+<\/jats:sup>\n                    transport from anion migration, lowers the Li\n                    <jats:sup>+<\/jats:sup>\n                    migration energy barrier, and homogenizes Li\n                    <jats:sup>+<\/jats:sup>\n                    flux across the electrolyte. Consequently, a stable LiF\/Li\n                    <jats:sub>2<\/jats:sub>\n                    S\u2010rich solid electrolyte interphase forms at the lithium metal interface, while continuous Li\n                    <jats:sup>+<\/jats:sup>\n                    supply mitigates solid\u2010solid interfacial polarization and accelerates reversible S\u2500C\/S\u2500S bond conversion and Li\n                    <jats:sub>2<\/jats:sub>\n                    S nucleation\/decomposition kinetics in SPAN cathodes. As a result, the solid\u2010state Li\u2010S batteries deliver a high reversible capacity of 1004.97 mAh g\n                    <jats:sup>\u22121<\/jats:sup>\n                    after 150 cycles at 0.2 C, prolonged cycling stability over 500 cycles at 1 C with a decay rate of \u223c0.06% per cycle, highlighting ion\u2010pair regulation via ionic\u2010liquid\u2010engineered MOF fillers as an effective pathway toward high\u2010performance solid\u2010state Li\u2010S batteries.\n                  <\/jats:p>","DOI":"10.1002\/anie.4252910","type":"journal-article","created":{"date-parts":[[2026,7,17]],"date-time":"2026-07-17T05:26:58Z","timestamp":1784266018000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Dynamic Ion\u2010Pair Networks Enable Selective Li\n                    <sup>+<\/sup>\n                    Transport for Stable and Efficient Solid\u2010State Lithium\u2010Sulfur Batteries"],"prefix":"10.1002","volume":"65","author":[{"given":"Haoyang","family":"Xiong","sequence":"first","affiliation":[{"name":"Guangdong Provincial Engineering Technology Research Center for Low Carbon and Advanced Energy Materials School of Electronic Science and Engineering (School of Microelectronics) South China Normal University  Foshan China"},{"name":"Institute of Carbon Neutrality Zhejiang Wanli University  Ningbo China"},{"name":"Ningbo Key Laboratory of High Energy Density Battery Yuyao Innovation Institute Zhejiang Wanli University Ningbo China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0094-8649","authenticated-orcid":false,"given":"Jiayi","family":"Wang","sequence":"additional","affiliation":[{"name":"Institute of Carbon Neutrality Zhejiang Wanli University  Ningbo China"},{"name":"Ningbo Key Laboratory of High Energy Density Battery Yuyao Innovation Institute Zhejiang Wanli University Ningbo 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