Aqueous　zinc-ion　batteries　(AZIBs)　are　promising　large-scale　energy　storage　devices　due　to　their　cost-effectiveness　and　high　safety.　However,　the　rampant　dendrite　growth　and　notorious　side　reactions　resulting　from　the　decomposition　of　active　water　molecules　hinder　its　practical　application.　Herein,　the　zincophilic　polyol-type　surfactant　of　alkyl　polyglycoside　(APG)　is　introduced　to　induce　the　rearrangement　of　the　H-bonds　network　to　diminish　the　free　water　activity,　facilitating　the　zinc-ion　solvation　structure　transition　from　[Zn2+(H2O)6·SO42–]　(solvent　separated　ion　pair,　SSIP)　to　[Zn2+(H2O)5·OSO32–]　(contact　ion　pair,　CIP)　with　less　Zn2+-solvated　H2O.　Meanwhile,　the　APG　molecular　preferentially　adsorb　on　the　Zn　surface　to　form　a　dehydrated　layer,　which　can　suppress　the　hydrogen　evolution　reaction　(HER)　and　hinder　the　two-dimensional　(2D)　diffusion　of　Zn2+　ions.　Consequently,　the　Zn//Zn　symmetric　cell　using　our　designed　electrolyte　demonstrates　an　ultralong　cycle　life　of　5250　h　at　1.0　mA　cm–2/1.0　mAh　cm–2.　Furthermore,　the　as-prepared　Zn//Na2V6O16·3H2O　full　cell　also　delivers　a　high-capacity　retention　rate　of　80.8%　even　after　1000　cycles　at　2.0　A　g–1,　superior　to　that　of　the　full　cell　using　pure　ZnSO4　electrolyte.　This　study　offers　an　effective　strategy　to　modulate　the　cation　solvation　structure　by　rearranging　the　H-bonds　network　for　a　highly　reversible　Zn　anode.　©　2024　Elsevier　B.V.