Efficient dynamic capture of radioiodine vapor from reprocessing of spent nuclear fuel under industrial conditions (∼423.15 K) is critically required due to its detrimental environmental and health impacts. However, conventional adsorbents often suffer from reduced binding affinity and structural degradation at elevated temperatures. To address these challenges, we have engineered a series of advanced polysulfate networks using sulfur (VI) fluoride exchange (SuFEx) click chemistry. These innovative networks integrate supramolecular macrocycle calix[4]pyrrole (C[4]P) and nitrogen-rich co-monomers as building blocks, and utilize polar sulfate bonds as important linkers, which provide availability of adsorptive sites and enhance the structural stability, thereby affording unexpected iodine capture performance at high temperatures. Among these SuFEx-derived materials, C[4]P-Azo exhibits exceptional iodine affinity through cooperative interactions involving multiple binding motifs, achieving an impressive iodine uptake capacity of 0.45 g g−1 at 423.15 K under dynamic adsorption conditions, setting a new benchmark in this field. Comprehensive characterizations and DFT calculations elucidate that advanced linker sulfate bonds enabling the marriage of C[4]P and N-rich monomers, play pivotal roles in facilitating iodine adsorption and maintaining structural integrity. These findings may pave the way for designing robust macrocyclic polysulfate-based adsorbents for dynamic radioiodine capture under industrial conditions.