Donor-acceptor　crystalline　hybrid　materials　are　a　new　type　of　photoactive　hybrid　complex　composed　of　two　semiconductor　components　at　the　molecular　level.　Naphthalenediimide　(NDI)　and　perylenediimide　(PDI)　based　donor-acceptor　crystalline　hybrid　materials　have　garnered　significant　interest　in　recent　years　owing　to　the　structural　diversity　of　the　inorganic　semiconductors　and　excellent　redox　activity　in　the　NDI/PDI,　which　can　effectively　achieve　long-lived　charge　separation　and　transfer　under　irradiation.　In　this　review,　we　summarize　recent　research　progress　in　the　construction　of　NDI/PDI-based　crystalline　hybrid　materials　using　POMs,　metal　halides,　and　transition-metal　ions,　and　their　applications　in　photochromism,　photo-controllable　fluorescence/phosphorescence,　photocatalytic　organic　transformations,　and　photothermal　conversion,　and　as　antibacterials,　to　provide　useful　guidance　for　the　design,　preparation　and　application　of　these　materials　in　the　future.　©　2024　Elsevier　B.V.