CdTe layers were grown on (001) GaAs substrates with a ZnSe buffer layer by molecular beam epitaxy. The high-quality ZnSe (001) epitaxy on GaAs allows us to control the II-VI/III-V heterovalent interface prior to the CdTe deposition. By subsequently adjusting the interface between ZnSe and CdTe, it was possible to selectively obtain the growth of either (001) or (111) CdTe epitaxial layers on the (0 0 1) ZnSe/GaAs substrate. Reflection high energy electron diffraction indicates that the nucleation of the CdTe epitaxial layers turns two-dimensional within a few seconds of initiating the growth. X-ray diffraction and photoluminescence measurements indicate that both the (111) and the (0 0 1) CdTe films are of high structural quality despite the large lattice constant mismatch of 14.6% between CdTe and the (001) ZnSe/GaAs substrate. Published by Elsevier B.V.