Natural polysaccharides have an important role in pharmaceutical industries and are considered a huge source and importance. Polysaccharides are biopolymers characterized by complex secondary structures performing several roles in plants, animals, and different other microorganisms. As it has versatility such as hydrophilicity, good stability, safety, lack of toxicity, and biodegradability in nature, some of them are extensively used for food packaging, pharmaceutical formulations, and various kind of sustainable and renewable goods in biomedical industries. In this context, we focused on natural polysaccharides from different sources such as plants, animals, algae, and microbes. Here, we concentrate on the chemical structures along with their commercial importance in the pharmaceutical industry. Moreover, a summary of the formulations and their applications in different natural polysaccharides has been highlighted in this review. Therefore, this study might be helpful for the development of not only different pharmaceutical formulations but also advantageous in food and biomedical industries in the future.