Polysaccharides are the most pervasive form of pharmaceutical excipients, consisting of diverse functional properties that play a vital role in sustaining life. Moreover, polysaccharides are well-known for several benefits such as nutritional benefits, effects on immunity, and delectability with biocompatibility. Natural polysaccharides are an assembly of monosaccharides’ long chain units bounded together with glycosidic linkage. In addition, polysaccharides are often quite heterogeneous, a slight alteration in the repeating unit produces distinct properties in biopolymers. Further engineered bio-based polymers produced to facilitate the regulated drug delivery system require information on structural conformation to meet the Food and Drug Administrative regulations. Furthermore, surface conformation and morphological imaging analysis are also of prime importance in the fabrication of drug delivery systems. Therefore, the amendment in the chemistry that brings about an alteration in the physicochemical property requires the use of various instrumental techniques for its characterization. In this chapter, a brief overview of compositional characterization techniques used for bio-based polymers is presented, focusing on analytical techniques that are generally applied. Moreover, the chapter promotes the application of suitable analytical techniques such as nuclear magnetic resonance spectroscopy, infrared spectroscopy, and varying chromatography in understanding the complex structure of polysaccharides. In addition, information on instruments used for surface morphological characterization of polymers is covered in this chapter.