Wurtzite ZnO nanowall structures have been synthesized on a (110) Al[sub 2]O[sub 3] substrate by a thermal evaporation and condensation method. The nanowalls are connected to each other and have a thickness of about 20–100 nm. An excellent epitaxial relationship with the substrate has been observed by X-ray diffraction. Edge-dislocation dipoles were observed by transmission electron microscopy. Photoluminescence measurements show strong UV emission at 390 nm for the white-gray nanowalls grown at high temperature, and very weak UV emission for the reddish nanowalls grown at low temperature.