Developing versatile sorption materials for radionuclide capture (e.g. iodine) is critical for nuclear energy and environmental science. Covalent organic frameworks (COFs) have recently become a new platform for developing sorption materials because of their high surface area and functionalised skeleton structure. Herein, two types of COF materials containing thiophene were designed as iodine sorbents and synthesised via a Schiff base reaction of benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene-2,5,8-tricarbaldehyde, benzidine (DADP) and p-phenylenediamine (DAB): DADP-COF and DAB-COF. DAB-COF exhibits a unique granular-rod-like morphology and has a higher surface area (1775 m2/g) than DADP-COF (1140 m2/g), which is clearly beneficial for the physical adsorption of iodine. Meanwhile, the COF backbone is rich in N and S sites, which are advantageous for the chemical adsorption of iodine. These two features make the two prepared COFs ideal iodine sorption materials. DAB-COF demonstrates an excellent gaseous iodine adsorption capacity of 4.2 g/g, ranking it as one of the most effective iodine sorption materials, while DADP-COF exhibits a good adsorption capacity of over 235 mg/g for iodine in cyclohexane solutions. Density functional theory calculations prove that imine N and thiophene S serve as active sites during the iodine adsorption. DAB-COF exposes more active sites because of its higher surface area, leading to a higher iodine adsorption capacity than DADP-COF. The results of this study indicate that introducing thiophene to COFs improves sorption efficacy for sorption applications in general and particularly paves the way for developing stable and effective COF sorbents for iodine capture from various environments.