Radioiodine is a challenging contaminant to remove from aqueous wastestreams, resulting from spent nuclear fuel reprocessing. To create a selective, economical adsorbent, a Cu-loaded bispicolylamine chelating resin was produced, from commercially available reagents and its performance for removal of aqueous iodide and iodine was assessed. The resin possessed a large equilibrium uptake capacity of 305 ± 14 mg.g−1 iodide and 2940 ± 180 mg.g−1 total iodine. Performance was close to maximal over a pH range of 2–10. Capacity was reduced by ~55% by the addition of cocontaminants nitrate and molybdate, but resistance to suppression was greatly superior to non-modified polyamine resins, clearly seen in dynamic column experiments. The uptake mechanism was investigated spectroscopically and was found to proceed via ligand-exchange, with some in-situ REDOX chemistry occurring, resulting in the formation of Cu(I) and triiodide. The latter was concurrently adsorbed on to the resin and occupied both strong (Cu-associated) and weak (charge-transfer complex formation) binding sites. Thermal decomposition of the loaded resins revealed that the captured iodine was volatised at several different temperatures, according to strength of adsorption, but a large fraction was converted to stable CuI, suggesting a possible pathway towards volume-reduction and immobilisation as a final wasteform.