The morphological, structural, and electrical properties of thick (8 ÷ 50 µm) CdTe epilayers grown on ZnTe/(100)GaAs by H2 transport vapour phase epitaxy (H2T‐VPE) are reported. Using a CdTe powder source temperature of 827 °C and a substrate temperature of 764 °C optimised CdTe epilayers were grown at atmospheric pressure with a smooth and almost featureless surface morphology. Mapping of the high resolution X‐ray diffraction intensity in the vicinity of the CdTe (400) reciprocal lattice point demonstrates that the samples are single crystalline and have negligible mosaicity contribution, supporting the epilayer high crystalline quality. Calibrated secondary ion mass spectrometry (SIMS) elemental depth profiles indicate that at the relatively high growth temperature of H2T‐VPE a complete interdiffusion between the thin ZnTe buffer and the overgrown CdTe crystal occur: ZnTe acts as a sacrificial layer …