The morphology and crystal structure of noble metal nano-films deposited on oxygen contaminated and oxygen-free Nb(001) surfaces have been studied with angle-resolved ultraviolet photoelectron spectroscopy, X-ray photo-electron diffraction, and reflection high energy electron diffraction. In the both cases a deposited noble metal film aligns its (211) direction with the [110] direction of the Nb(001) surface. But, while a noble metal grows on an oxygen contaminated Nb(001) surface with the hexagonal close-packed (hcp) (111) planes parallel to the surface (i.e. in the (111)-oriented face centred cubic phase (fcc)), on a non-contaminated Nb(001) it grows with its hcp planes perpendicular to the surface. The latter happens because in the initial stages of the epitaxy the first two monolayers (MLs) of the noble metal grow pseudomorphically on a contamination-free Nb(001). The pseudomorphic layer is strongly extended parallel to the Nb(001) surface in comparison to its natural fcc (001) plane. As a consequence of the atomic volume conservation principle the out-of-plane lattice of the pseudomorphic layer is contracted. Thus, its body centred tetragonal (110) planes, which stay perpendicular to the surface, contract into denser-packed planes, i.e. in hcp ones. In the direction perpendicular to the surface, where the substrate does not have a direct influence on the film, the pseudomorphic layer relaxes into its natural close-packed phase, i.e. into hcp atomic planes. These planes appear as soon as the third pseudomorphic ML begins to grow. The stacking axis of the planes lies in the (100) surface of Nb and is locked by it. The fact that thick nano-films of Cu (up to 50 MLs), Ag and An (up to 100 MLs) grow in the (1120)-oriented hcp phase can be attributed to a much better fit of the hcp than of fcc stacking sequence to the four-fold symmetry of the Nb(001) surface. (c) 2005 Elsevier B.V. All rights reserved.