The major discovery here is a robust and water-stable metal organic framework (MOP) material capable of reversible binding of the volatile and reactive molecules of ICI and I-2. The immobilization of 12 and ICI, as well as their controllable release thus achieved, is to facilitate the wide-ranging applications of these volatile species as catalysts and reagents in chemical and industrial processes. The framework material TMBP center dot CuI (hereafter TCuI) can be conveniently prepared in quantitative yields by heating CuI and the organic linker TMBP (3,3',5,5'-tetramethyl-4,4'-bipyrazol) in acetonitrile. The microporous three-dimensional net of TCuI features CuI chains that contribute to efficient and reversible binding of ICI and 12 molecules, to result in the stoichiometrically well-defined adducts of TCuI center dot ICl and TCuI center dot I-2, respectively. Moreover, the confinement of a volatile compound like ICI within the MOF medium provides unique opportunities to enhance its reactivity and selectivity as a chemical reagent, as is exemplified by the iodination reactions examined herein. With this exemplary study, we intend to stimulate interest in further exploring MOFs and other porous media (e.g., porous polymers) for entrapping ICI and other volatile reagents (e.g., Br-2 SCl2, S2Cl2, and SOCl2) and for potentially novel reactivity associated with the porous medium.