By introducing a thin MgO/TiN buffer, layer‐by‐layer growth of ZnO epilayer on Si(111) has been realized. ZnO film directly on Si(111) substrate is poly‐crystallized, whereas its quality could be significantly improved by inserting the buffer layer. In the case of employing the buffer layer, in situ reflection high‐energy electron diffraction demonstrates that ZnO film is epitaxy and proceeding in the layer‐by‐layer growth mode. High‐resolution X‐ray diffraction indicates the relationship is ZnO(0002)//MgO(111)//Si(111) (out‐of‐plane) and the ZnO (0002) peak with the full width at half maximum of 1.3°. High‐resolution transmission electron microscopy further validates that the in‐plane epitaxial relationship is ZnO//MgO//Si. In photoluminescence, epitaxy ZnO film shows clear exciton‐related peaks, which are believed to be of high quality. Copyright © 2014 John Wiley & Sons, Ltd.