We have studied the structure and the photoluminescence of Mn-passivated nanocrystalline ZnO thin films. The ZnO thin films were prepared by thermally oxidizing ZnS:Mn films grown by low-pressure metalorganic chemical vapor deposition. The structural properties of the ZnO films were examined by X-ray diffraction and X-ray photoelectron spectroscopy. It was demonstrated that the Mn passivation could dramatically change the emission characteristics of nanocrystalline ZnO thin films. The photoluminescence spectra of the films with an optimized Mn-doped concentration showed only ultraviolet emission, while the green emission was fully quenched due to the Mn passivation of the ZnO nanocrystallite surface. A core-shell structure model of the surface passivation is presented. The note of the oxygen vacancy (Vo**) as the dominant recombination center for green emission is discussed. (C) 2003 Published by Elsevier Science B.V.