Low-dimensional　inorganic-organic　hybrid　perovskites　with　high　moisture　tolerance　and　long-lived　charge　separation　states　have　captured　significant　attention　in　the　field　of　optoelectronic　devices.　To　further　achieve　the　relationship　between　crystal　structures　and　stability,　as　well　as　charge　separation　behaviors,　three　one-dimensional　hybrid　perovskites　containing　electron-deficient　naphthalene　diimide　ammonium　(NDIEA)　and　electron-rich　iodoplumbate　chains,　[(H2NDIEA)Pb2I6]·2DMF　(1),　[(H2NDIEA)2Pb5I14·(DMF)2]·4DMF　(2),　and　[(HNDIEA)2Pb2I6]·3H2O　(3),　were　synthesized.　Crystal　structure　determinations　revealed　various　synthesis　conditions　leading　to　different　stacking　modes,　especially　the　inorganic　lead　iodide　fraction,　which　resulted　in　different　water　resistances　and　charge-separated　behaviors.　The　comprehensive　analysis　found　that　strong　intermolecular　interactions　(anion−π　interactions　and　π-π　interactions),　and　matching　energy　levels　between　protonated　NDIEA　and　iodoplumbate　chains,　can　facilitate　the　generation　of　long-lived　charge　separation　states　and　extraordinary　moisture　stability,　even　in　the　water　environment.　In　addition,　the　conductivity　behavior　of　3　was　also　explored　in　detail.　©　2023　American　Chemical　Society.