X-ray photoelectron spectroscopy and x-ray excited Auger electron spectroscopy have been used to investigate the electronic core levels of mercury chalcogenophosphate HgPS3 and HgPSe3 single crystals. On the basis of the measured chemical shifts relative to the elements information on the bonding state of the compositional atoms has been deduced. Single peak structures have been observed for the analyzed Hg, P, S, and Se core levels. As happens in CdPS3 and ZnPS3 the Hg 5d levels are discrete and well localized. This analogy confirms the validity of the transition-metal weakly interacting model already used satisfactorily for interpreting the optical properties of these chalcogenophosphates. © 2000 American Vacuum Society.