The　reversibility　and　stability　of　aqueous　zinc‐ion　batteries　(AZIBs)　are　largely　limited　by　water‐induced　interfacial　parasitic　reactions.　Here,　dimethyl(3,3‐difluoro‐2‐oxoheptyl)phosphonate　(DP)　is　introduced　to　tailor　primary　solvation　sheath　and　inner‐Helmholtz　configurations　for　robust　zinc　anode.　Informed　by　theoretical　guidance　on　solvation　process,　DP　with　high　permanent　dipole　moments　can　effectively　substitute　the　coordination　of　H2O　with　charge　carriers　through　relatively　strong　ion‐dipolar　interactions,　resulting　in　a　water‐lean　environment　of　solvated　Zn2+.　Thus,　interfacial　side　reactions　can　be　suppressed　through　a　shielding　effect.　Meanwhile,　lone‐pair　electrons　of　oxygen　and　fluorinated　features　of　DP　also　reinforce　the　interfacial　affinity　of　metallic　zinc,　associated　with　exclusion　of　neighboring　water　to　facilitate　reversible　zinc　planarized　deposition.　Thus,　these　merits　endow　the　Zn　anode　with　a　high‐stability　performance　exceeds　3800 hours　at　0.5 mA cm−2　and　0.5 mAh cm−2　for　Zn||Zn　batteries　and　a　high　average　Coulombic　efficiency　of　99.8 %　at　4 mA cm−2　and　1 mAh cm−2　for　Zn||Cu　batteries.　Benefiting　from　the　stable　zinc　anode,　the　Zn||NH4V4O10　cell　maintains　80.3 %　of　initial　discharge　capacity　after　3000 cycles　at　5 A g−1　and　exhibits　a　high　retention　rate　of　99.4 %　against　to　the　initial　capacity　during　the　self‐discharge　characterizations.