A novel ultralight crystalline hybrid composite material, IPcomp-7, was developed for highly efficient sequestration of radioiodine. This material combines amino-functionalized Zr(IV)-MOP with imine-functionalized COF, resulting in a composite with hierarchical porosity, multifunctional binding sites, and high surface area. IPcomp-7 exhibits exceptional iodine adsorption capacities of 9.98 g·g⁻¹ in vapor phase and 4.74 g·g⁻¹ in aqueous phase, with fast kinetics, high retention efficiency, and reusability. The material's unique structure enables strong charge-transfer interactions with iodine, facilitated by its cationic nature, free Cl⁻ ions, and heteroatom functionalities. The composite demonstrates high selectivity for iodine, even in the presence of other anions, and shows excellent performance in both vapor and aqueous phases. It also exhibits rapid and efficient recovery of iodine, with over 97% release efficiency in the first cycle. The material's hierarchical porosity and low density enable rapid mass transfer and efficient iodine capture. The study highlights the potential of IPcomp-7 for practical applications in nuclear waste management, water purification, and medical uses. The material's performance is supported by various characterization techniques, including XRD, FT-IR, XPS, and NMR, which confirm its structural and functional properties. The results demonstrate the effectiveness of the hybrid composite in capturing iodine, with high adsorption capacities and selectivity, making it a promising candidate for iodine sequestration applications.A novel ultralight crystalline hybrid composite material, IPcomp-7, was developed for highly efficient sequestration of radioiodine. This material combines amino-functionalized Zr(IV)-MOP with imine-functionalized COF, resulting in a composite with hierarchical porosity, multifunctional binding sites, and high surface area. IPcomp-7 exhibits exceptional iodine adsorption capacities of 9.98 g·g⁻¹ in vapor phase and 4.74 g·g⁻¹ in aqueous phase, with fast kinetics, high retention efficiency, and reusability. The material's unique structure enables strong charge-transfer interactions with iodine, facilitated by its cationic nature, free Cl⁻ ions, and heteroatom functionalities. The composite demonstrates high selectivity for iodine, even in the presence of other anions, and shows excellent performance in both vapor and aqueous phases. It also exhibits rapid and efficient recovery of iodine, with over 97% release efficiency in the first cycle. The material's hierarchical porosity and low density enable rapid mass transfer and efficient iodine capture. The study highlights the potential of IPcomp-7 for practical applications in nuclear waste management, water purification, and medical uses. The material's performance is supported by various characterization techniques, including XRD, FT-IR, XPS, and NMR, which confirm its structural and functional properties. The results demonstrate the effectiveness of the hybrid composite in capturing iodine, with high adsorption capacities and selectivity, making it a promising candidate for iodine sequestration applications.