This article provides a detailed account of the principles, instrumentation,and applications of x-ray photoelectron spectroscopy (XPS), a technique used for elemental and compositional analysis of surfaces and thin films. It reviews the nomenclature of energy states and sensitivity of electrons at the surface that are capable of producing peaks in XPS. Additionally, it presents information on the instrumentation and the preparation and mounting of samples for XPS analysis. The article explains qualitative analysis, namely, measuring of shifts in the binding energy of core electrons, multiplet splitting, and the Auger parameter; and quantitative analysis such as depth analysis carried out using XPS. It also discusses the applications of XPS with examples.