Combined hard x-ray photoelectron spectroscopy (HAXPES) and electrical characterisation measurements have been shown to provide complementary information on the electrical performance of Si and GaAs based metal-oxide-semiconductor (MOS) structures. The results obtained indicate that surface potential changes at the semiconductor/dielectric interface due to the presence of different work function metals can be detected from HAXPES measurements. Changes in the semiconductor band bending at zero gate voltage and the flat band voltage values derived from C-V measurements are in agreement with the semiconductor core level shifts measured from the HAXPES spectra. These results highlight the potential application of this measurement approach in the evaluation of the efficacy of surface passivation treatments: HAXPES hard x-ray photoelectron spectroscopy; C-V capacitance voltage; D-it-interface state density; BE binding energy, at reducing defect states densities in MOS structures. (C) 2014 Elsevier B.V. All rights reserved.