X-ray Photoelectron Spectroscopy of large bandgap or insulating material surfaces relies on an effective mechanism that compensates for the emission (loss) of electrons by maintaining the material surface at a steady-state uniform potential. While a steady-state may be attained by utilizing an active compensation, such as low power electron emitting filament, there is the possibility that the surface potential is not uniform over the area analyzed, leading to peak shifts and incorrect spectral interpretation. In this work, a spectral data processing method based on mapping the ZrO2 and Pd/ZrO2 surfaces utilizing photoemission peak binding energy is proposed, which provides information about the response of specific material surfaces to charge compensation. Spectromicroscopy of ZrO2 and Pd/ZrO2 surfaces without spatial information is used to monitor the efficacy of charge compensation. Exploiting counts distributed over many bins require the use of procedures and algorithms essential to practical mapping peak positions. Iterative singular value decomposition is therefore introduced and utilized as a means of efficiently delivering spatially resolved spectra from which binding energy for peaks is computed. The concepts developed in this work result in robust and accurate peak models of ZrO2 and Pd/ZrO2 that can be applied in XPS analysis of not only ZrO2 but other large bandgap or insulating material surfaces. Supporting arguments for a peak model representing signal from Zr 3p and Pd 3d are developed within this work are presented.