This book provides a theoretical background to X-ray photoelectron spectroscopy (XPS) and a practical guide to the analysis of the XPS spectra using the RxpsG software, a powerful tool for XPS analysis. Although there are several publications and books illustrating the theory behind XPS and the origin of the spectral feature, this book provides an additional practical introduction to the use of RxpsG. It illustrates how to use the RxpsG software to perform specific key operations, with figures and examples which readers can reproduce themselves. The book contains a list of theoretical sections explaining the appearance of the various spectral features (core‐lines, Auger components, valence bands, loss features, etc.). They are accompanied by practical steps, so readers can learn how to analyze specific spectral features using the various functions of the RxpsG software. This book is a useful guide for researchers in physics, chemistry, and material science who are looking to begin using XPS, in addition to experienced researchers who want to learn how to use RxpsG. In the digital format, the spectral data and step-by-step indications are provided to reproduce the examples given in the textbook. RxpsG is a free software for the spectral analysis. Readers can find the installation information and download the package from https://github.com/GSperanza/ website. RxpsG was developed mainly by Giorgio Speranza with the help of his colleague dr. Roberto Canteri working at Fondazione Bruno Kessler. Key Features: Simplifies the use of RxpsG, how it works, and its applications. Demonstrates RxpsG using a reproduction of the graphical interface of RxpsG, showing the steps needed to perform a specific task and the effect on the XPS spectra. Accessible to readers without any prior experience using the RxpsG software. Giorgio Speranza is Senior Researcher at Fondazione Bruno Kessler – Trento Italy, Associate Member of the Italian National Council of Research, and Associate Member of the Department of Industrial Engineering at the University of Trento, Italy.