p‐type doping of Zn1‐xMgx Te has been investigated by metalorganic vapour phase epitaxy using tris‐dimethylaminophosphorus as a dopant source. The photoluminescence (PL) and electrical properties of the as‐grown and post‐annealed layers have been clarified as a function of the dopant transport rate. In PL spectra at 4.2 K, the strong donor acceptor pair emission vanished and instead enhancement of P acceptor‐related excitonic emission and/or appearance of free‐to‐bound emission were observed for all the layers by the post‐annealing treatment. In accordance with the PL behavior, the hole concentration at room temperature of the annealed layers was significantly enhanced from 2×1015∼2×1016 cm‐3 to 5×1016∼2×1018 cm‐3 by a maximum factor of ∼600. The enhanced hole concentration shows saturation tendency with increasing dopant transport rate. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)