Organic-inorganic　hybrid　iodobismuthate　perovskites　have　become　promising　semiconductive　materials　for　their　environmentally　friendly　and　light-harvesting　characteristics.　However,　their　low-dimensional　bismuth-iodide　skeletons　result　in　poor　charge-separation　efficiency,　limiting　their　application　in　optoelectronic　devices.　To　address　this　issue,　the　donor-acceptor　(D-A)　heterostructures　have　been　introduced　to　the　iodobismuthate　hybrid　materials　by　incorporating　an　electron-deficient　N,N′-bis(4-aminoethyl)-1,4,5,8-naphthalene　diimide　(NDIEA)　as　the　electron　acceptor　and　organic　counterpart.　Five　naphthalenediimide/iodobismuthate　hybrid　heterostructures,　named　(H2NDIEA)1.5·Bi2I9·3DMF　(1),　H2NDIEA·[Bi2I8(DMF)2]·2DMF　(2),　(H2NDIEA)2·Bi4I16·2H2O·4MeOH　(3),　(H2NDIEA)2·Bi4I16·8H2O　(4),　and　[(H2NDIEA)2·Bi6I22]n·4nH2O　(5)　(DMF　=　N,N-dimethylformamide),　were　synthesized.　Their　crystal　structures,　water　stabilities,　charge-separated　behaviors,　and　electrical　properties　have　been　studied　through　experimental　and　computational　investigations.　The　results　revealed　that　hybrids　3-5　exhibited　high　water　resistance　attributed　to　their　tightly　packed　structures　and　robust　H-bonds　between　solvent　molecules　and　organic-inorganic　supramolecular　frameworks.　Density　functional　theory　calculations　confirmed　characteristic　type-IIa　band　alignments　of　all　the　five　hybrids,　facilitating　to　the　photoinduced　charge　separation.　Moreover,　the　closer　contact　caused　by　the　strong　anion−π　interactions　between　electron　donors　and　acceptors　in　hybrid　5　leads　to　the　long-lived　charge-separated　states　and　improved　electrical　properties　compared　to　the　other　hybrids.　©　2023　American　Chemical　Society.