In this paper, we report on the synthesis and structure of hierarchical zinc oxide nanotubes. Hierarchical nanotubes grown by physical vaporization of zinc in the presence of a catalyst were decorated with many secondary zinc oxide nanorods on the outer surface. The axis of these nanotubes with an average diameter of 65 nm was aligned along the c axis of wurtzite zinc oxide. The hierarchical zinc oxide nanotubes, many of which were single crystals, were transparent or opaque, depending on whether they had a zinc layer inside. The opaque nanotubes showed an abrupt change in electronic transmittance during investigation with transmission electron microscopy. The unique structure of the hierarchical ZnO nanotubes and the quantum effect resulting from the reduced dimension will modify the original properties of ZnO, leading to novel applications.