The surface Fermi level of semi-insulating and n(+)-type GaAs(0 0 1) was determined before and after passivation with n-alkanethiol self-assembled monolayers (SAMs) by X-ray photoelectron spectroscopy. Fermi level positioning was achieved using Au calibration pads integrated directly onto the GaAs surface, prior to SAM deposition, in order to provide a surface equipotential binding energy reference. Fermi level pinning within 50meV and surface barrier characteristics according to the Advanced Unified Defect Model were observed. Our results demonstrate the effectiveness of the Au integration technique for the determination of band-edge referenced Fermi level positions and are relevant to an understanding of emerging technologies based on the molecular-semiconductor junction. (C) 2010 Elsevier B. V. All rights reserved.