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Abstract Boron trifluoride (BF₃) is a highly corrosive gas widely used in industry. Confining BF₃in porous materials ensures safe and convenient handling and prevents its degradation. Hence, it is highly desired to develop porous materials with high adsorption capacity, high stability, and resistance to BF₃corrosion. Herein, we designed and synthesized a Lewis basic single‐crystalline hydrogen‐bond crosslinked organic framework (H_COF‐50) for BF₃storage and its application in catalysis. Specifically, we introduced self‐complementaryortho‐alkoxy‐benzamide hydrogen‐bonding moieties to direct the formation of highly organized hydrogen‐bonded networks, which were subsequently photo‐crosslinked to generate H_COFs. The H_COF‐50 features Lewis basic thioether linkages and electron‐rich pore surfaces for BF₃uptake. As a result, H_COF‐50 shows a record‐high 14.2 mmol/g BF₃uptake capacity. The BF₃uptake in H_COF‐50 is reversible, leading to the slow release of BF₃. We leveraged this property to reduce the undesirable chain transfer and termination in the cationic polymerization of vinyl ethers. Polymers with higher molecular weights and lower polydispersity were generated compared to those synthesized using BF₃ ⋅ Et₂O. The elucidation of the structure–property relationship, as provided by the single‐crystal X‐ray structures, combined with the high BF₃uptake capacity and controlled sorption, highlights the molecular understanding of framework‐guest interactions in addressing contemporary challenges. 

Olefin-rich hydrogen-bonded crosslinked organic frameworks (H_COFs) were crosslinkedviafree radical reactions and subsequently converted to a hydroxylated H_COF.