Abstract Organic frameworks face a trade‐off between the framework stability and the bond dynamics, which necessitates the development of innovative linkages that can generate stable frameworks without hindering efficient synthesis. Although iodine(I)‐based halogen‐bonded organic frameworks (XOFs) have been developed, constructing XOFs based on bromine(I) is desirable yet challenging due to the high sensitivity of bromine(I) species. In this work, we present the inaugural construction of stable bromine(I)‐bridged two‐dimensional (2D) halogen‐bonded organic frameworks, XOF(Br)−TPy−BF 4 /OTf , based on sensitive [N⋅⋅⋅Br⋅⋅⋅N] + halogen bonds. The formation of XOF(Br)−TPy−BF 4 /OTf was monitored by 1 H NMR, XPS, IR, SEM, TEM, HR‐TEM, SEAD. Their framework structures were established by the results from PXRD, theoretical simulations and SAXS. More importantly, XOF(Br) displayed excellent chemical and thermal stabilities. They exhibited stable two‐dimensional framework structures in various organic solvents and aqueous media, even over a wide pH range (pH 3–12), while the corresponding model compounds BrPy 2 BF 4 /OTf decomposed quickly even in the presence of minimal water. Furthermore, the influence of the counterions were investigated by replacing BF 4 with OTf, which improved the stability of XOF(Br). This characteristic enabled XOF(Br) to serve as an efficient oxidizing reagent in aqueous environments, in contrast with the sensitivity of BrPy 2 BF 4 /OTf , which performed well only in organic media. This study not only deepens our fundamental understanding of organic frameworks but also opens new avenues for the development and application of multifunctional XOFs.

Halogen‐Bonded Organic Frameworks (XOFs) Based on N⋯Br+⋯N Bonds: Robust Organic Networks Constructed by Fragile Bonds