Inspired by “micro/nanoreactor” effect of cellular organelle on specific biochemical reactions, a double honeycomb‐like hierarchical capsule confined encapsulation with functional micro/nanocrystals is designed. The bioinspired hierarchical capsules derived from polymeric composite microspheres are successfully fabricated through a combination of selective chemical etching and pyrolysis. In situ introduction of functional guests (including organometallic molecules, tetraethoxysilane, or metal–organic frameworks (MOFs)) into internal cellular structure of microspheres is first put forward by phase inversion method. The development of selective etching creates honeycomb‐like structure on the outside surface of capsule and allows sulfur to homogeneously distribute into matrix. With the novel approach, the hierarchical channels (micro–meso–macropore) of composite capsule enhance transportation of reactants and dispersion of active sites, and thus exhibit superior photocatalytic oxidation and electromagnetic absorbing. The promising strategy will be applied more generally to encapsulate different species into hierarchical capsule with tailored properties and functionalities.
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