X-ray photoelectron spectroscopy (XPS) is a spectroscopic technique in the family of electron spectroscopies, that is, those methods whose probe consists of electrons instead of photons. In the case of XPS, a soft, usually monochromatic X-ray causes the emission of electrons by means of the photoelectric effect. Differences in chemical potential and/or polarizability of the molecules can cause an alteration of the binding energy; in addition to photoelectrons, an ordinary XPS spectrum may also contain Auger electrons. In an XPS system, an electron gun is used to deliver a low-energy electron flux with a low current over the illuminated spot. In an XPS instrument, an ion gun may be used with two main purposes: the simpler one is to neutralize the electron excess over the analyzed area. From a practical standpoint, the laboratory XPS technique is used mainly to characterize materials and surfaces of various nature.