Zinc oxide nanopowders were synthesized by the sol-gel method from an ethanol solution of zinc acetate dihydrate. Detailed structural and microstructural investigations were carried out using x-ray diffraction, Raman spectroscopy, thermogravimetric and differential thermal analyses, as well as high-resolution transmission electron microscopy (TEM) and field-emission scanning electron microscopy. The intermediate compound of the reaction was layered zinc hydroxide acetate that further transforms into hexagonally shaped ZnO crystalline nanoplates (d(m) = 4 nm), which aggregate into larger spherical particles. According to the TEM analysis the ZnO nanoparticles were self-assembled into larger particles with the same orientation, i.e. aligned lattice planes of the particles. A further solvothermal treatment resulted in hexagonal, prismatic ZnO mesocrystals.