Abstract The structural properties, crystalline quality and surface morphology of CdTe thin films without and with a ZnTe buffer layer grown on (001)GaAs by molecular beam epitaxy (MBE) have been studied. CdTe thin film directly prepared on GaAs substrate displays (111) orientation with an island growth mode, whereas the CdTe epilayers with a ZnTe buffer are (001)-oriented single-crystalline film with a two-dimensional (2D) growth mode. The morphology and surface root-mean-square (RMS) roughness of CdTe epilayers are also dramatically improved by using a ZnTe buffer. Furthermore, it is suggested that the high-temperature (HT) ZnTe buffer grown at 360 °C is more efficient for enhancing CdTe structural quality than the low-temperature (LT) one at 320 °C. The CdTe epilayer on the HT-ZnTe buffer shows a narrower full-width at half-maximum (FWHM) of double-crystal X-ray rocking curve (DCXRC) for (004) reflection and a smaller RMS roughness.