We report on the optical characterization by photoluminescence and reflectivity of AlxGa1–xN/GaN high electron mobility transistor structures. The samples studied were grown either by molecular beam epitaxy or metal‐organic vapor phase epitaxy, on silicon (111) or sapphire (0001) substrates. We focus on a broad luminescence band, shown to be related to the GaN cap layer (surface quantum‐well) and its injection intensity dependence. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)