Efficiently capturing fluorocarbons, potent greenhouse gases with high global warming potentials (GWP), remains a daunting challenge due to limited effective approaches for constructing high-performance adsorbents. To tackle this issue, we have pioneered a novel strategy of developing radical porous materials as effective adsorbents for fluorocarbon capture. The resulting radical covalent triazine framework (CTF), CTF-azo-R, shows exceptional fluorocarbon (perfluorohexane, a representative model pollutant among fluorocarbons) uptake capacity of 270 wt %, a record-high value among all porous materials reported to date. Spectral characteristics, experimental studies, and theoretical calculations indicate that the presence of stable radicals in CTF-azo-R contributes to its superior fluorocarbon capture performance. Furthermore, CTF-azo-R demonstrates exceptionally high chemical and thermal stabilities that fully meet the requirements for practical applications in diverse environments. Our work not only establishes radical CTF-azo-R as a promising candidate for fluorocarbon capture but also introduces a novel approach for constructing advanced fluorocarbon adsorbents by incorporating radical sites into porous materials. This strategy paves the way for the development of radical adsorbents, fostering advancements in both fluorocarbon capture and the broader field of adsorption and separation.