We report on epitaxial growth of ZnO on (112) orientated CuInS2 thin films. Step-by-step growth and investigation by photoelectron spectroscopy (PES) and low energy electron diffraction (LEED) provided information on the growth mode and the electronic structure of the ZnO-CuInS2-interface. During the initial growth no ZnO is deposited. instead a monolayer of ZnS is formed by depletion the CuInS2 surface of excess sulfur. Thereafter, the ZnO growth starts on the ZnS buffer layer. The band alignment derived from PES shows that the ZnS buffer layer is thin enough to provide a beneficial band alignment for photovoltaic applications. (C) 2009 Published by Elsevier B.V.