Stilbene cross-linked pillar [5]arene-based polymer adsorbents synthesized via Friedel−Crafts polymerization reactions are able to capture a high amount of iodine vapor up to ∼1.8 gg −1 . UV−vis spectroscopic analysis revealed that the synthesized polymer adsorbents rapidly adsorb iodine from water, which has significant implications in environmental remediation and nuclear safety.