Efficient,　green,　and　economical　removal　of　radioactive　iodine　(I2)　has　drawn　worldwide　attention　for　the　safe　development　of　nuclear　energy.　Metal-organic　frameworks　(MOFs)　have　been　demonstrated　to　be　potential　candidates　for　I2　capture.　Herein　we　report　the　synthesis　of　two　novel　isomeric　MOFs　bearing　stilbene　moieties　for　exceptionally　high　I2　adsorption.　[Cd(hsb-2)(tsbdc)]·0.5DMF　(HSB-W8)　and　Cd(hsb-2)(tsbdc)　(HSB-W9),　which　exhibit　two-dimensional　and　twofold　interpenetrated　three-dimensional　structures,　respectively,　have　been　assembled　from　hydrogenated　Schiff　base　ligands,　hsb-2　(1,2-bis(4′-pyridylmethylamino)-ethane)　and　trans-stilbene-4,4-dicarboxylate　(tsbdc),　and　Cd(NO3)2　by　the　diffusion　method.　Such　isomers　arise　from　the　different　conformations　of　hsb-2　ligands　controlled　by　diffusion　temperatures.　The　π-electron-rich　stilbene　moieties　render　these　Cd-MOFs　ideal　platforms　for　I2　capture.　The　adsorption　capacities　of　HSB-W8　and　HSB-W9　in　I2　vapor　at　room　temperature　can　reach　up　to　2.32　and　1.92　g　g−1,　respectively,　which　are　comparable　to　the　best-performing　MOF　materials　reported　so　far.　Furthermore,　pseudo-second-order　(PSO)　kinetic　model　analysis,　Fourier　transform　infrared　(FT-IR)　spectroscopy,　Raman　spectral　analysis,　density　functional　theory　(DFT)　calculations,　and　control　experiments　were　performed　to　shed　light　on　host-guest　interactions　and　the　iodine　adsorption　mechanism.　This　work　develops　a　rational　strategy　to　design　and　synthesise　functional　MOF　materials　for　iodine　adsorption.　©　2022　The　Royal　Society　of　Chemistry.