AbstractAdsorption‐based iodine (I₂) capture has great potential for the treatment of radioactive nuclear waste. In this study, we apply a “multivariate” synthetic strategy to construct ionic covalent organic frameworks (iCOFs) with a large surface area, high pore volume, and abundant binding sites for I₂ capture. The optimized material iCOF‐AB‐50 exhibits a static I₂ uptake capacity of 10.21 g g⁻¹ at 75 °C and a dynamic uptake capacity of 2.79 g g⁻¹ at ≈400 ppm I₂ and 25 °C, far exceeding the performances of previously reported adsorbents under similar conditions. iCOF‐AB‐50 also exhibits fast adsorption kinetics, good moisture tolerance, and full reusability. The promoting effect of ionic groups on I₂ adsorption has been elucidated by experimentally identifying the iodine species adsorbed at different sites and calculating their binding energies. This work demonstrates the essential role of balancing the textural properties and binding sites of the adsorbent in achieving a high I₂ capture performance.