Organic　carbonyl　compounds　as　electrode　materials　have　exhibited　promising　candidates　for　application　in　next-generation　aqueous　rechargeable　batteries.　However,　a　primary　concern　that　is　poor　cycling　performance　are　still　remains　due　to　high　solubility　of　discharge　products,　which　greatly　limits　their　broader　application.　Herein,　we　developed　a　strategy　to　enhance　the　cyclability　of　aqueous　zinc-organic　batteries　(AZOBs)　by　the　terminal　imidization　and　lateral　π-system　extension　of　perylene-3,4,9,10-tetracarboxylic　dianhydride　(PTCDA).　This　strategy　resulted　in　a　perylene-based　imide　derivative　with　larger　π-conjugated　structure　(2PDI),　significantly　inhibiting　the　solubility　in　an　aqueous　electrolyte.　As　expected,　2PDI　as　cathode　offered　a　discharge　capacity　of　72.8　mA　h　g−1　at　a　current　density　of　100　mA　g−1,　and　even　retaining　99.4%　capacity　after　ultralong　50　000　cycles　at　3000　mA　g−1.　Its　mechanism　of　reversible　co-insertion　Zn2+/H+　at　the　carbonyl　site　was　verified　via　electrochemical　tests　and　ex-suit　characterizations.　Moreover,　density　functional　theory　calculation　(DFT)　also　revealed　this　co-insertion　mechanism.　©　2023　Elsevier　B.V.