X-ray Photoelectron Spectroscopy (XPS) is a well-known analytical technique which gives conclusive information about the elemental composition, chemical state and electronic structure of materials, especially at their surfaces. A detailed description on the working, fundamental principles, data analysis, interpretation and some of the XPS spectrum of chalcogenide-based crystals grown adopting Bridgman-Stockbarger technique is discussed in this chapter. The description given here can be used as a common reference medium for the budding researchers to have a basic idea about the XPS analysis.