The　application　of　zinc-metal-based　batteries　is　hindered　by　the　low　thermodynamic　stability　of　zinc　anodes　and　the　sluggish　desolvation　kinetics　of　the　interfacial　[Zn(H2O)6]2+　complex,　which　can　induce　serious　side　reactions　and　exacerbate　dendrite　formation.　Herein,　an　innovative　catalytic　desolvation　mechanism　is　proposed　to　manipulate　the　interfacial　solvation　structure　by　engineering　a　π-electron-rich　(C=O/C=N　configurations)　covalent　organic　polymer　(COP)　layer　as　an　interfacial　catalyst.　It　was　revealed　that　the　π-electrons　can　trigger　dissociation　of　the　[Zn(H2O)6]2+　complex　through　an　ortho-synergistic　reaction　process,　which　includes　a　nucleophilic　reaction　between　electron-accepting　C　atoms　at　C=O/C=N　sites　and　H2O　molecules　and　an　electrophilic　reaction　between　electron-donating　sites　near　O　and　N　heteroatoms　and　Zn2+.　In　situ　characterization　analysis　combined　with　advanced　theoretical　calculations　confirmed　that　such　a　catalytic　desolvation　process　can　dynamically　induce　contact　ion　pairs　and　aggregate　dominated　interfacial　solvation　structures,　boosting　Zn2+　diffusion　and　deposition　kinetics.　Consequently,　suppressed　side　reactions　and　homogenous　(002)-crystal-preferred　Zn2+　deposition　can　be　simultaneously　achieved.　Therefore,　an　excellent　cycling　lifespan　of　2500　h　was　obtained　for　the　symmetric　Zn　cell　and　an　ultra-stable　cycling　lifespan　of　28　000　cycles　for　full　cells.　We　believe　that　this　catalytic　desolvation　strategy　will　pave　a　new　avenue　in　the　interfacial　design　of　Zn　anodes.　©　2025　The　Royal　Society　of　Chemistry.