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Chemical structuring of bulk materials is fraught with imperfection resulting from inherent defects and inhomogeneities. Nanocrystals, on the other hand, are remarkable for their crystalline perfection and controllable chemical behavior. In her Perspective, Buriak discusses results reported in the same issue by Yin et al. on the fabrication of hollow nanostructures by means of a phenomenon known as the Kirkendall effect. In this synthesis route, one reactant diffuses quickly into another, leaving behind vacancies that fuse into larger voids. With nanocrystalline materials, the result is precisely formed nanostructures, a finding that may have implications for fundamental nanochemistry and for applications of structured compounds.