The safe and efficient capture of radioactive iodine is highly necessary, but still remains an ongoing challenge. Herein, because of its special layer structure, CuBi–CO3-layered double hydroxides (CuBi–CO3-LDHs) are used to serve as a generic platform, and 3D hierarchical flowerlike ZIF-67/CuBi–CO3-LDH composites are synthesized by a simple coprecipitation method. After immobilization, the flowerlike morphology of CuBi–CO3-LDHs can be completely preserved and proved by scanning electron microscope. Various affecting factors on adsorption performance are investigated, including adsorbent dose, initial concentration of iodine, and temperature. The experimental and modeling results manifest that iodine adsorption is accurately elucidated by pseudo-second-order model, and the equilibrium isotherm is accordant with the Freundlich model. Moreover, the regeneration experiment indicates that ZIF-67/CuBi–CO3-LDH composites possess good stability and reusability for the removal of iodine. The possible adsorption mechanisms of iodine on ZIF-67/CuBi–CO3-LDHs involve particular layer structure and the strong interaction between nitrogen of imidazole ring and iodine, which were investigated by X-ray diffraction, energy-dispersive X-ray, and X-ray photoelectron spectroscopy spectra. The good performance for the iodine adsorption indicates that ZIF-67/CuBi–CO3-LDHs may be identified as a promising adsorbent in the field of iodine capture.