Polysaccharides are used in a wide range of applications across the medical, food, and material science spheres. Their applicability is in part a consequence of their specific surface properties and the nature of their interactions at interfaces. Intensive research into polysaccharide surface properties and methods to investigate these has been undertaken for decades. Due to the complicated structural, chemical, and physical features of polysaccharides, however, fully understanding their surface properties and developing effective methods for studying these properties are still challenging tasks. In this chapter methods frequently used for polysaccharide surface characterization, including sample preparation and surface analysis, are described and critically discussed. In addition to the traditionally used methods, several novel techniques of preparing polysaccharide model surfaces and description of advanced instrumentation for this purpose are presented. Several examples of how surface modification of polysaccharides measured using these methods may be practically applied are also discussed.