X-ray photoelectron spectroscopy is a powerful tool for the characterization of molecular and hybrid solar cells. This technique allows for atomic-level characterization of their components as well as for the determination of the electronic structure that governs the key conversion processes. In this chapter, we introduce the basic concepts of electronic structure in molecules and semiconducting materials followed by a description of the concepts of photoelectron spectroscopy and how they relate to electronic structure. Finally, we give examples of the application of photoelectron spectroscopy to different types of molecular and hybrid solar cell materials demonstrating the type of information that can be obtained, to gain fundamental understanding and to further develop such devices
