ZnTe thin films on sapphire substrate with nanofaceted structure have been studied. The nanofaceted structure of the m-plane (10-10) sapphire was obtained by heating the substrate at above 1100°C in air, and the r-plane (10-12) and S-plane (1-101) were confirmed. ZnTe layers were prepared on the nanofaceted m-plane sapphire substrates by molecular beam epitaxy (MBE). The effect of the nanofaceted structure on the orientation of the thin films was examined based on x-ray diffraction (XRD) pole figures. Transmission electron microscopy (TEM) was also employed to characterize the interface structures. The ZnTe layer on the nanofaceted m-plane sapphire substrate exhibited (331)-plane orientation, compared with (211)-plane without the nanofaceted structure. After thermal treatment, the m-plane surface vanished and (211) layer could not be formed because of the lack of surface lattice matching. On the other hand, (331)-plane thin film was formed on the nanofaceted m-plane sapphire substrate, since the (111) ZnTe domains were oriented on the S-facet. The orientation of the ZnTe epilayer depended on the atomic ordering on the surface and the influence of the S-plane.