Despite its potential as a clean power source to meet rising electricity demands, nuclear energy generates radioactive waste, including isotopes of iodine, that pose significant environmental and health risks. There is a growing demand to capture radioactive iodine and repurpose it effectively. However, achieving this dual functionality with a single material remains a significant challenge. This study explores phosphorus‐based porous organic polymers (P‐POPs) as probes for these dual functionalities. By employing 4‐formyl(triphenyl)phosphine (BB1) and phenyl‐1,4‐diacetonitrile (BB2) under the Knoevenagel polycondensation method, P‐POPs (PKPOPs) have been synthesized that exhibit a smooth spherical morphology, which efficiently capture and release iodine under ambient conditions, facilitating efficient transportation of molecular iodine. This novel approach aims to potentially transform nuclear waste into valuable organic feedstock via an iodination reaction. The innovative application of PKPOP has also been demonstrated for iodination reactions using ball mills and under continuous flow conditions, showcasing its potential for safer waste management and utilization.