Every year, new organisms that survive and colonize adverse environments are discovered and isolated. Those organisms, called extremophiles, are distributed throughout the world, both in aquatic and terrestrial environments, such as sulfurous marsh waters, hydrothermal springs, deep waters, volcanos, terrestrial hot springs, marine saltern, salt lakes, among others. According to the ecosystem inhabiting, extremophiles are categorized as thermophiles, psychrophiles, halophiles, acidophiles, alkalophilic, piezophiles, saccharophiles, metallophiles and polyextremophiles. They have developed chemical adaptation strategies that allow them to maintain their cellular integrity, altering physiology or improving repair capabilities; one of them is the biosynthesis of extracellular polysaccharides (EPS), which constitute a slime and hydrated matrix that keep the cells embedded, protecting from environmental stress (desiccation, salinity, temperature, radiation). EPS have gained interest; they are explored by their unique properties such as structural complexity, biodegradability, biological activities, and biocompatibility. Here, we present a review concerning the biosynthesis, characterization, and potential EPS applications produced by extremophile microorganisms, namely, thermophiles, halophiles, and psychrophiles. A bibliometric analysis was conducted, considering research articles published within the last two decades. Besides, an overview of the culture conditions used for extremophiles, the main properties and multiple potential applications of their EPS is also presented.