Ultrathin layers of N‐face GaN(000$ \bar 1 $) on c‐plane sapphire have been grown via plasma assisted molecular beam epitaxy (PAMBE) and investigated in‐situ via reflection of high energy electron diffraction (RHEED), Xray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Our studies of the electronic interface between substrate and adsorbate reveal a band offset about (1.7 ± 0.1) eV at the GaN‐sapphire interface and an additional band bending of the GaN layer of 0.4 eV within the first 3 nm. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)