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Bacterial exopolysaccharides have enormous diversity with valuable characteristics, synthesized by various pathways in extreme conditions like salinity, geothermal springs, or hydrothermal vents. Due to extreme environments, these microorganisms have various adaption principles (eg, low pH, high temperature, high saltation, and high radiation). Exopolysaccharide is an organic compound produced by most bacteria during fermentation using various carbon sources, resulting in a jelly-like or mass network structure outside the cell wall. This biopolymer has an adherent cohesive layer throughout the cell layer. Hot spring bacterial polysaccharides contain diverse extracellular polymeric substances. With a gain in popularity in applications of thermophilic microbial polysaccharides and its demand in diverse value-added industrial products, this chapter aims to provide valuable information on the physicochemical …