This article focuses on the principles and applications of X-ray photoelectron spectroscopy (XPS) for the analysis of elemental and chemical composition. The discussion covers the nomenclature, instruments, and specimen preparation process of XPS. Some of the factors pertinent to the calibration of materials for accurate measurements using XPS are provided, along with some aspects of the accuracy in quantitative analysis by XPS. In addition, the article presents examples of how XPS data can be used to solve problems with surface interactions.