Polysaccharides are important biomolecules synthesized by microbes and termed as exopolysaccharides (EPS) when secreted outside the microbial cell. The EPS structure is essential for various biological processes like cell interaction, cell adhesion, and molecular recognition, which plays an important role in immune modulation. The EPS employ the toll-like receptor of the macrophage to stimulate using MAP kinase pathway signaling and NF-κB. It also advocates NK cells cytotoxicity. These EPS are secreted by bacteria, green algae, microalgae, and fungi. The property of the microbial cell to modulate the immune system is currently a matter of global importance that can be applied in industry such as food, pharmaceutical, and textile. One of the major advantages of working with EPS in the commercial field is that the microbial growth parameters can be regulated as per requirement for maximum production of the desired products. In the pharmaceutical industry, EPS application for treatment of infectious diseases to overcome the lack of medicinal supplements has resulted in an exponential demand for such immunomodulators. These biochemical molecules stabilize the immune system by influencing the humoral or cellular immune system through suppression or stimulation. They modulate pathophysiological processes to prevent diseases. These potent immune modulators have been further utilized in the food industry. The EPS derived from microbes are mostly utilized as emulgent, stabilizer, and thickener. These exopolysaccharides and its consequent products have been widely utilized for preparing bakery products, beverages, dairy products, and coatings. This chapter gives an insight on EPS contribution in the pharmaceutical industry by modulating the immune system along with the enhancement of immunity as well as in the food industry as preservation and functional food.