The most significant and renewable class of polymeric materials are extracellular exopolysaccharides (EPSs) produced by microorganisms. Because of their diverse chemical and structural makeup, EPSs play a variety of functions in a variety of industries, including the agricultural industry, dairy industry, biofilms, cosmetics, and others, demonstrating their biotechnological significance. EPSs are typically utilized in high-value applications, and current research has focused heavily on them because of their biocompatibility, biodegradability, and compatibility with both people and the environment. Due to their high production costs, only a few microbial EPSs have been commercially successful. The emergence of financial barriers and the growing significance of microbial EPSs in industrial and medical biotechnology has increased interest in exopolysaccharides. Since exopolysaccharides can be altered in a variety of ways, their use is expected to increase across a wide range of industries in the coming years. This review introduces some significant EPSs and their composites while concentrating on their biomedical uses.