We have developed a simple solid-vapor approach for controlled growth of the tetraleg ZnO nanostructure at high yield. The length of the tetraleg is 2–3 mm and the edge size of its centering nucleus is 70–200 nm. Our electron microscopy study gives the first direct evidence about the existence of the octahedral multiple twin nucleus, which is confirmed to be responsible for the formation of the tetraleg ZnO nanostructure. The tetraleg ZnO nanostructure is likely to be a candidate as building blocks for contructing photonic crystals. q 2003 Elsevier Science Ltd. All rights reserved.