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This perspective summarizes the recent progress in the design of frustrated packing structures in nanoparticle, polymer, and polymer nanocomposite systems for the controlled formation of microporosity. The presence of size disparity and shape anisotropy among structural units, coupled with the interaction between structural units, can lead to the phenomenon of packing frustration. The strategy offers possible solutions for the synergy of mechanical property and porosity, paving the way for potential applications in gas adsorption\/separation and ion conduction. 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