Hierarchically Porous Organic Cages

Abstract Imparting mesopores to organic cages of an intrinsic microporous nature to build up hierarchically porous cage soft materials is a grand challenge and will reshape the property and application scope of traditional organic cage molecules. Herein, we discovered how to engineer mesopores into microporous organic cages via their host–guest interactions with long chain ionic surfactants. Equally important, the ionic head of surfactants equips the supramolecularly assembled porous structures with charge‐selective uptake and release function in solution. Interestingly, such hierarchically porous organic cage can serve as a nanoreactor once trapping enzymes within the cavity, which show 5‐fold enhanced activity of enzymatic catalysis when compared with the free enzymes.