The metalorganic vapour phase epitaxy of ZnTe on single crystal (100)ZnTe:P wafers is reported. The technological steps to prepare a substrate surface suitable for the high quality homoepitaxy of ZnTe are identified and optimised in terms of structural and morphological properties of overgrown epilayers. Removal of ∼7 µm of material from the ZnTe:P wafers by chemical etching in 1% Br2‐methanol solution proved necessary to achieve a sufficiently smooth and homogeneous surface; in‐situ H2 heat treatment of the wafers at 350°C immediately before growth ensures optimal desorption of residual oxides, allowing epilayer crystalline quality comparable to the substrate. However, the structure of epilayers degrades for growth temperatures (TG) above 350 °C due to the occurrence of stacking faults (SFs) within ∼200‐300 nm from the epilayer‐substrate interface. Accordingly, the epilayer band‐edge luminescence …