A novel multilayer comb-like Zinc oxide nanostructure has been successfully synthesized via pure Zn chemical vapor deposition on anodic aluminum oxide substrate at 950°C. X-ray diffraction and selected area electron diffraction indicate that the nanocombs are of wurtzite structure and single crystalline. The morphology and the microstructure of the nanocombs are investigated by the scanning electron microscopy. Transmission electron microscopy shows the growth direction, and energy-dispersive X-ray spectroscopy reveals the atomic composition ratio of Zn/O. The growth mechanism of such interesting and unique morphologies is briefly discussed.