Lately, a series of adsorbents with conjugated structures were developed and found to be efficient for the removal of seriously hazardous radionuclide iodine. Herein, we present designed two novel cyclophosphazene-based electron-enriched π-conjugation hybrid polymers on the basis of the Friedel-Craft alkylation cross-linking strategy between hexachlorocyclotriphosphazene and thiophene or pyrrole, which was correspondingly abbreviated as CPP-Tp and CPP-Pyr. CPP-Tp and CPP-Pyr displayed excellent volatile iodine capture capacity up to 346 wt% and 297 wt%, respectively. Remarkably, in spite of the poor porosity, CPP-Tp presented outstanding iodine capture capacity per unit BET surface area up to 68 wt% comparing to the known iodine adsorbents to date, due to the strong chemical affinity between iodine molecules and the electron-enriched groups (heteroatoms and π-conjugated heterocyclic rings) in the frameworks. Besides, both CPP-Tp and CPP-Pyr showed rapid adsorption rate and high removal efficiency towards iodine in hexane solutions, and the maximum iodine adsorption capacities were also correspondingly calculated to be 588 mg/g and 625 mg/g for CPP-Tp and CPP-Pyr according to the Langmuir model. In addition, both CPP-Tp and CPP-Pyr exhibited favorable regeneration and recycle ability, indicating the cyclophosphazene-based conjugated CPP-Tp and CPP-Pyr might become one of potential candidates for the removal of iodine in the future.