The article presents the development of an ultralight crystalline hybrid composite material for the efficient sequestration of radioiodine. The material, named IPcomp-7, is fabricated by covalently linking amino-functionalized Zr(IV)-metal-organic polyhedra (MOP) with a dual-pore containing imine-functionalized covalent organic framework (COF). This hybrid composite exhibits a hierarchical macro-micro porosity, large surface area, and multi-functional binding sites, which collectively enhance its interaction with iodine. IPcomp-7 demonstrates ultra-high vapor and aqueous-phase iodine adsorption capacities of 9.98 g/g and 4.74 g/g, respectively, with fast adsorption kinetics, high retention efficiency, reusability, and recovery. The material's performance is attributed to its unique structural features, including high crystallinity, large surface area, and the presence of heteroatoms and dense N-containing moieties. The study also investigates the adsorption mechanism, showing strong interactions between iodine and the composite's functionalities, such as imine, amine groups, and cationic nature with free Cl ions. The hybrid composite's effectiveness is further demonstrated through dynamic column-based iodine capture experiments, where it efficiently removes iodine from water and vapor phases. The research highlights the potential of IPcomp-7 for practical applications in nuclear waste management and water purification.The article presents the development of an ultralight crystalline hybrid composite material for the efficient sequestration of radioiodine. The material, named IPcomp-7, is fabricated by covalently linking amino-functionalized Zr(IV)-metal-organic polyhedra (MOP) with a dual-pore containing imine-functionalized covalent organic framework (COF). This hybrid composite exhibits a hierarchical macro-micro porosity, large surface area, and multi-functional binding sites, which collectively enhance its interaction with iodine. IPcomp-7 demonstrates ultra-high vapor and aqueous-phase iodine adsorption capacities of 9.98 g/g and 4.74 g/g, respectively, with fast adsorption kinetics, high retention efficiency, reusability, and recovery. The material's performance is attributed to its unique structural features, including high crystallinity, large surface area, and the presence of heteroatoms and dense N-containing moieties. The study also investigates the adsorption mechanism, showing strong interactions between iodine and the composite's functionalities, such as imine, amine groups, and cationic nature with free Cl ions. The hybrid composite's effectiveness is further demonstrated through dynamic column-based iodine capture experiments, where it efficiently removes iodine from water and vapor phases. The research highlights the potential of IPcomp-7 for practical applications in nuclear waste management and water purification.