Aqueous　zinc　ion　batteries　(AZIBs)　are　promising　for　large-scale　energy　storage　due　to　the　advantages　of　high　safety,　high　theoretical　capacity,　and　cost-effectiveness.　However,　the　stability　of　AZIBs　is　poor　(generally　50–100　cycles)　at　low　current　densities　due　to　side　reactions.　Here,　choline　glycerophosphate　(CGP)　is　introduced　as　a　zwitterion　additive　to　improve　performance　of　AZIBs.　The　CGP　helps　to　form　a　new　solvated　structure　of　Zn2+,　named　zwitterion-separated　ion　pair　(ZSIP)　structure　that　can　link　OTf−　ion　and　repel　H2O　molecular.　In　addition,　CGP　can　be　adsorbed　on　anode　to　suppress　formation　of　by-products　ZnxOTfy(OH)2x-y·nH2O,　and　on　cathode　to　inhibit　Zn3(OH)2V2O7·2H2O　phase　generation.　Consequently,　the　Zn||Cu　cell　shows　an　excellent　average　Coulombic　efficiency　of　99.79%　over　800　cycles　at　1 mA　cm−2　and　0.5　mAh　cm−2.　Impressively,　the　Zn//NH4V4O10　battery　demonstrates　exceptional　capacity　retention　of　95%　along　with　a　high　specific　capacity　of　409.3　mAh　g−1　after　350　cycles　under　a　trickle　(dis)charge　process　(0.2　A　g−1)　and　an　ultra-long　lifespan　of　14 000　cycles　at　5　A　g−1　along　with　a　high　specific　capacity　of　217　mAh　g−1.　The　concept　of　ZSIP　opens　a　new　avenue　for　developing　aqueous　batteries　with　high　performance　and　long　stability　in　the　future.　©　2024　Wiley-VCH　GmbH.