We report the observation of a novel nanostructured growth mode of the ceramic spinel zinc aluminate grown on c-sapphire in the form of epitaxially ordered twinned crystallites with pronounced vertically aligned “nanoblades” on top of these crystallites. The nanostructures are formed on bare c-sapphire substrates using a vapour phase transport method. Electron microscopy images reveal the nanostructure morphology and dimensions and allow direct and indirect observation of the twin boundary location in a number of samples. The nanoblade structure with sharply rising sidewalls gives rise to a distinctive bright contrast in secondary electron images in scanning electron microscopy measurements.