**Abstract**

Graphene and graphite are two widely studied carbon materials. Due to their particular properties and structure, graphene and graphite have been used in a variety of fields such as electronic devices and sensors. The surface properties of graphene and graphite as well as their derivatives are strongly connected to the performances of devices and sensors. Thus, it is necessary to choose appropriate surface analysis techniques for characterization, which are not only useful in the understanding of the surface composition and structure but also in the design and development of these types of materials. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) have been two of the key surface analysis techniques that are widely used to characterize these surfaces. In this chapter, an overview of the applications of XPS and ToF-SIMS in the study of the surfaces of graphene and graphite is present. We hope that the information provided will simulate more exciting and inspiring research on graphene and graphite and promote practical applications of these carbon materials in the future.

**Keywords:** graphene, graphite, surface, XPS, ToF-SIMS
