Graphene-like nanostructures, solely or in combination with redox active compounds, are an important component of battery electrodes. Design of effective electrode materials requires a deep understanding of electrochemical reactions occurring at graphene surfaces. The methods of X-ray photoelectron spectroscopy (XPS) are very helpful in such research, providing the composition of studied samples and electronic state of individual elements. In this chapter, we demonstrate advantages of XPS for monitoring of chemical vapor deposition graphene growth and lithium penetration under graphene layers, disclosing of interactions with metals and interface states.