Donor-acceptor　(D-A)　alignment　that　integrates　D-A　pairs　into　the　modular　and　versatile　crystalline　metal-organic　frameworks　is　a　powerful　strategy　to　precisely　fabricate　multifunctional　materials　with　unique　optoelectronic　properties　and　applications　at　the　molecular　level.　Herein,　we　reported　an　unprecedented　threefold　interpenetrating　D-A　hybrid　framework　by　incorporating　an　electron-deficient　linear　viologen　zwitterion　into　the　lead-halide　systems.　The　1D　iodoplumbate　nanoribbon　and　interpenetrating　close-packed　D-A　structure　endowed　this　hitherto　unknown　semiconductive　alignment　with　the　anisotropic　conductivity　and　high　stability.　When　used　in　a　thermal　sensor,　it　presented　exceptional　electrical　properties　with　a　high　sensitivity　(high　thermal　index　B　of　4671　K)　and　decent　temperature　coefficient　of　resistivity　(0.72%　°C-1)　in　wide　operational　temperature　ranges　(40-220　°C),　which　are　among　the　best　of　the　related　thermistors.　This　work　develops　a　pathway　to　bridge　the　gaps　between　hybrid　materials　and　electron　devices.　©　2022　American　Chemical　Society.　All　rights　reserved.