Prebiotics are non-digestible food ingredients that beneficially impact the host by promoting the growth and activity of beneficial gut microbiota. Extracellular polysaccharides (EPS) have recently garnered significant attention for their potential benefits, which include resistance to dehydration, protection against nonspecific and specific host immunity, and adherence. The molecular structure, degree of polymerization, and source of EPS are diverse. As a microbial byproduct, in direct contrast to the polysaccharides of food grade, the production of microbial EPS can be scaled up concerning industrial demands. The intestinal microbiome is vital in supporting an individual’s health by enhancing gut integrity, diminishing inflammation, and nurturing a nutrient-rich environment. The energy and carbon for intestinal microflora are provided by EPS which also serves as the short-chain fatty acids (SCFAs) producer, a chief metabolic end-product such as acetate, propionate, and butyrate. These metabolic end-products are vital for intestinal health, aiding as a source of energy for colonocytes, controlling immune responses, managing inflammation, maintaining gut integrity, and encompassing the extra-intestinal benefits. This chapter reviews current knowledge on the structure-specific functions of EPS, highlighting their probable role in endorsing gut health and providing promising therapeutic possibilities in supervising gastrointestinal disorders. The findings also recommend capable avenues for rising formulations of dietary EPS or designing innovative EPS structures to enhance intestinal integrity.