AbstractGaN/Al0.12Ga0.88N and Ga0.99Gd0.01N/Al0.12Ga0.88N multi‐quantum well samples with the quantum well thickness of one nm were grown by a radio‐frequency plasma‐assisted molecular‐beam epitaxy on GaN (0001) templates. The epitaxial growth is established in the grown samples. Gd doped multi‐quantum well samples show magnetic behaviour at room temperature. Photoluminescence measurements show a strong photoluminescence at the higher energy side of GaN excitonic peak for the GaN multi‐quantum wells. A new luminescence peak at 3.598 eV was found for Gd doped GaN multi‐quantum wells. This photoluminescence peak is attributed to the formation of an exciton–polaron in the distorted regions around the Gd dopants in GaN multi‐quantum wells. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)