A size-controlled Zn(OH)(2) template is used as a case study to explain the chemical strategy that can be executed to chemically engineering various nanoscale cavities. Zn(OH)(2) octahedron with 8 vertices and 14 edges is fabricated via a low temperature solution route. The size can be tuned from 1 to 30 μm by changing the reaction conditions. Two methods can be selected for the hollow process without loss of the original shape of Zn(OH)(2) template. Ion-replacement reaction is suitable for fabrication of hollow sulfides based on the solubility difference between Zn(OH)(2) and products. Controlled chemical deposition is utilized to coat an oxide layer on the surface of Zn(OH)(2) template. The abundant hydroxyl groups on Zn(OH)(2) afford strong coordination ability with cations and help to the coating of a shell layer. The rudimental Zn(OH)(2) core is eliminated with ammonia solution. In addition, ZnO-based heterostructures possessing better chemical or physical properties can also be prepared via this unique templating process. Room-temperature photoluminescence spectra of the heterostructures and hollow structures are also shown to study their optical properties.