Herein, covalent organic polyrotaxane xerogels (COPRs), were developed as comprehensive and recyclable “three birds with one stone” platform effectively handling organic/radioactive iodine pollutants challenges. COPRs were synthesized rapidly from β-ketoenamine and aromatic amines β-cyclodextrin (β-CD) inclusion via Michael addition-elimination reaction in water at room temperature and pressure, avoiding the usage of any organic solvents. The formation of β-CD inclusion significantly increases the solubility and reactivity of monomers in water. The threading of β-CD endows multiple absorption sites within the porous skeleton, improving its iodine capture capacity. The integration of β-CD ring throughout the carbon skeleton not only provides a green and ultra-low-cost approach for preparing COPRs with brand-new structure, but also offers direct and effective methods realizing the carbon neutrality from the source of production. This work could be used as a general method for the specifically modifying COPs, providing opportunities to meet the growing needs of society.