In X-ray Photoelectron Spectroscopy (XPS), binding energies and intensities of core level peaks are commonly used for chemical analysis of solid surfaces, after subtraction of a background signal. This background due to photoelectron energy losses to electronic excitations in the solid (surface and bulk plasmon excitation, inter band transitions) contains valuable information related to the near surface dielectric function epsilon((h) over bar omega). In this work, the sensitivity of Photoelectron Energy Loss Spectroscopy (PEELS) is investigated using a model system, namely the well-controlled surface reconstruction of diamond. Boron-doped microcrystalline thin films with a mixture of (1 1 1) and (1 0 0) preferential orientations were characterized in the as-grown state, with a partially hydrogenated surface, and after annealing at 1150 degrees C in ultra high vacuum. After annealing, the bulk (sigma + pi) plasmon of diamond at 34.5 eV is weakly attenuated but no evidence for surface graphitization is observed near 6 eV, as confirmed by electronic properties. Unexpected features which appear at 10 +/- 1 eV and 19 +/- 1 eV in the energy loss distribution are well described by simulation of surface plasmon excitations in graphite-like materials; alternatively, they also coincide with experimental inter band transition losses in some graphene layers. This comparative study shows that the PEELS technique gives a clear signature of weak effects in the diamond surface reconstruction, even in the absence of graphitization. It confirms the sensitivity of PEELS acquisition with standard XPS equipment as a complementary tool for surface analysis. (C) 2013 Elsevier B.V. All rights reserved.