The synthesis of nanocrystalline ZnO by thermal decomposition of zinc hydroxyacetate, Zn(5)(OH)(8)(CH(3)CO(2))(2)·nH(2)O, was investigated. The decomposition process was examined using X-ray diffraction, thermogravimetric analysis, mass spectrometry, electron microscopy, Brunauer-Emmett-Teller surface area analysis, and solid-state NMR spectroscopy. Intermediate Zn(5)(OH)(8)(CH(3)CO(2))(2)·nH(2)O phases form at temperatures up to 110 °C from the starting compound Zn(5)(OH)(8)(CH(3)CO(2))(2)·2H(2)O by partial dehydration. At ∼110 °C, 4 equiv of ZnO and 1 equiv of Zn(CH(3)CO(2))(2) are formed. Further heating causes Zn(CH(3)CO(2))(2) to decompose to acetone, acetic acid, acetic anhydride, and ZnO. Notably, a portion of Zn(CH(3)CO(2))(2) sublimes during the process. Overall, the product of the calcination is equiaxed ZnO nanocrystals of 20-100 nm diameter.