A noncontact chemical and electrical measurement X-ray photoelectron spectroscopy (XPS) technique is performed to investigate a CdS-based photoresistor during its operation. The main objective of the technique is to trace chemical- and location-specified surface potential variations as shifts of the XPS Cd 3d(5/2) peak position without and under photoillumination with four different lasers. The system is also modeled to extract electrical information. By analyzing the measured potential variations with this model, location-dependent resistance values are represented (i) two dimensionally for line scans and (ii) three dimensionally for areal measurements. In both cases, one of the dimensions is the binding energy. The main advantage of the technique is its ability to assess an element-specific surface electrical potential of a device under operation based on the energy deviation of core level peaks in surface domains. Detection of the variations in electrical potentials and especially their responses to the energy of the illuminating source in operando, is also shown to be capable of detecting, locating, and identifying the chemical nature of structural and other types of defects.