Irreversible　Zn　plating/stripping　along　with　interfacial　degradation　seriously　affect　the　practical　applications　of　aqueous　zinc-ion　batteries.　Herein,　3-(hydroxy(phenyl)phosphoryl)propanoic　acid　(HPA)　is　introduced　as　an　electrolyte　additive　that　constructs　a　spherical　micellar　molecular　network　via　association　of　amphiphilic　groups　and　multiple　coordination　sites　to　directionally　adsorb/transfer　Zn2+　in　aqueous　electrolyte,　thus　serving　as　an　ion-flow　stabilizer.　Moreover,　the　strong　adsorption　between　HPA　and　the　zinc　surface　induces　the　formation　of　an　in　situ　organic-inorganic　hybrid　solid　electrolyte　interphase　layer,　which　further　promotes　the　charge　transfer　kinetics　and　suppresses　interfacial　parasitic　reactions.　As　a　result,　an　ultra-high　average　Zn　plating/stripping　efficiency　of　99.91%　over　2100　cycles　at　4　mA　cm−2　is　achieved.　Additionally,　the　symmetrical　cell　with　HPA　exhibits　outstanding　reversibility　at　an　unprecedentedly　high　current　density　of　120　mA　cm−2.　Surprisingly,　the　initial　coulombic　efficiency　of　Zn//Cu　cell　is　71.74%　after　7-day　calendar　aging,　which　is　better　than　a　cell　without　HPA　(42.59%).　Furthermore,　the　Zn//MnO2　cell　exhibits　superior　capacity　retention　of　80%　after　1100　cycles　at　2　A　g−1　compared　to　the　cell　without　HPA　(37%).　This　study　provides　an　in-depth　insight　into　understanding　the　molecular　network　regulation　of　aqueous-based　electrolytes,　thus　shedding　light　on　a　universal　approach　toward　ultra-stable　battery　applications.　©　2024　The　Royal　Society　of　Chemistry.