Sodium　metal　batteries,　known　for　their　high　theoretical　specific　capacity,　abundant　reserves,　and　promising　low-temperature　performance,　have　garnered　significant　attention.　However,　the　large　ionic　radius　of　Na+　and　sluggish　transport　kinetics　across　the　interfacial　structure　hinder　their　practical　application.　Previous　reviews　have　rarely　regulated　electrolyte　performance　from　the　perspective　of　anions,　as　important　components　of　the　electrolyte,　the　regulation　mechanism　is　not　well　understood.　Herein,　a　novel　anion　receptor　additive,　4-aminophenylboronic　acid　pinacol　ester　(ABAPE),　is　proposed　to　weaken　the　coupling　between　anions　and　cations　and　accelerate　Na+　transport　kinetics.　The　results　of　theoretical　calculations　and　X-ray　photoelectron　spectroscopy　with　deep　Ar-ion　etching　demonstrate　that　the　introduction　of　this　additive　alters　the　solvation　structure　of　Na+,　reduces　the　desolvation　barrier　and　forms　a　stable　and　dense　electrode-electrolyte　interface.　Moreover,　ABAPE　forms　hydrogen　bonds　(−NH　⋅　⋅　⋅　O/F)　with　H2O/HF,　effectively　preventing　the　hydrolysis　of　NaPF6　and　stabilizing　acidic　species.　Consequently,　the　Na||Na　symmetric　cell　exhibits　excellent　long-cycle　performance　of　500　h　at　1　mA　cm−2　and　0.5　mAh　cm−2.　The　Na||Na3V2(PO4)3　(NVP)　cell　with　the　addition　of　ABAPE　maintains　a　capacity　retention　of　84.29　%　at　1　C　after　1200　cycles　and　presents　no　capacity　decay　over　150　cycles　at　−40　°C.　©　2024　Wiley-VCH　GmbH.