Aqueous　zinc　ion　batteries　are　gaining　popularity　due　to　their　high　energy　density　and　environmental　friendliness.　However,　random　deposition　of　zinc　ions　on　the　anode　and　sluggish　migration　of　zinc　ions　on　the　interface　would　lead　to　the　growth　of　zinc　dendrites　and　poor　cycling　performance.　To　address　these　challenges,　we　developed　a　fluorinated　solid-state-electrolyte　interface　layer　composed　of　Ca5(PO4)3F/Zn3(PO4)2　via　an　in　situ　ion　exchange　strategy　to　guide　zinc-ion　oriented　deposition　and　fast　zinc　ion　migration　on　the　anode　during　cycling.　The　introduction　of　Ca5(PO4)3F　(FAP)　can　increase　the　nucleation　sites　of　zinc　ions　and　guide　the　oriented　deposition　of　zinc　ions　along　the　(002)　crystal　plane,　while　the　in　situ　formation　of　Zn3(PO4)2　during　cycling　can　accelerate　the　migration　of　zinc　ions.　Benefited　from　our　design,　the　assembled　Zn//V2O5　⋅　H2O　batteries　based　on　FAP-protected　Zn　anode　(FAP-Zn)　achieve　a　higher　capacity　retention　of　84　%　(220　mAh　g−1)　than　that　of　bare-Zn　based　batteries,　which　have　a　capacity　retention　of　23　%　(97　mAh　g−1)　at　3.0　A　g−1　after　800　cycles.　This　work　provides　a　new　solution　for　the　rational　design　and　development　of　the　solid-state　electrolyte　interface　layer　to　achieve　high-performance　zinc-ion　batteries.　©　2023　Wiley-VCH　GmbH.