In this paper we have determined the role of oxidizing pressure and annealing temperature in the formation of ZnO nanostructures on the Mo surface. ZnO has been grown on Mo(001) by means of physical vapor deposition of Zn in molecular oxygen pressure. Combining STM, XPS, and XRD we have studied the relation between morphology, composition, and structure. ZnO grows as a film with (101¯1) preferential orientation up to a thickness of 10 Ã, catalyzed by the Mo surface that provides oxygen available for oxide formation and limited by the residual polarity of the surface. Increasing the deposited amount, the role of the Mo interface becomes less effective, and part of the Zn remains metallic, forming clusters on the surface that catalyze the fu...