Here we report that easily obtained per-ethylated pillar[6]arene (EtP6) is a new adsorbent for iodine capture with high chemical and thermal stability. Nonporous EtP6 solids are shown to capture not only volatile iodine in the air but also iodine dissolved in an organic solvent and aqueous solution. Uptake of iodine leads to a structural transformation of EtP6 in the solid state. In the single crystal structure of iodine-doped EtP6 (I2@EtP6), each adsorbed iodine molecule is located between two adjacent EtP6 molecules to form a linear supramolecular polymer. Iodine is released spontaneously from I2@EtP6 solids when they are immersed in cyclohexane. These EtP6 solids can be reused many times without losing iodine capture capacity.