A new microstructure, thornball, of zinc oxide (ZnO) was synthesized by a very simple solid vapor deposition process under lead oxide (PbO) atmosphere. The microthornballs consist of numerous needles, which extend outwards in all directions symmetrically. They have dimensions of 120 mu m in diameter, while the average diameter of the needles is about 100-200 nm. The needles on the balls grow along the (0 0 0 1) orientation and have gradient compositions along radial. Control experiments proved that PbO played an important role in the growth. Additionally, photoluminescence property was observed and provided the evidence that PbO did not deteriorate the optical properties of ZnO thornballs. This kind of microstructures has potential applications in the field of photochemical catalysis. (c) 2005 Elsevier Ltd. All rights reserved.