The interaction of zinc and faceted MgO(111) thin films prepared on a Mo(110) substrate was investigated in situ by using various surface analysis techniques, including X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, Auger electron spectroscopy, high-resolution electron energy loss spectroscopy, and low-energy electron diffraction. The results revealed that three-dimensional Zn islands exist on the faceted MgO(111) films and that no chemical interaction takes place at the interface at room temperature. Initially, deposited Zn is stable at temperatures below 400 K and diffuses into MgO at temperatures above 425 K. A portion of Zn is oxidized at similar to 10(-6) mbar O-2 at room temperature. An interfacial phase of ZnxMg1-xO was formed after Zn was exposed to similar to 10(-6) mbar O-2 at temperatures >= 500 K. The faceted structure on the MgO(111) surface is of a disadvantage for the epitaxial growth of ZnO films.