In the course of the discovery of novel polysaccharides of biotechnological interest, it is now widely accepted that extremophilic microorganisms will provide a valuable resource not only for exploitation in novel biotechnological processes but also as models for investigating how biomolecules are stabilized when subjected to extreme conditions. Microbes isolated from extreme environments offer a great diversity in chemical and physical properties of their EPS as compared to anywhere else in the biosphere. Bacteria from remote areas still remain virtually unexplored and there is not doubt that extreme environments are a rich source of microorganisms of biotechnological importance. A number of interesting and unique bacterial polysaccharides have been isolated from these ecosystems and are expected to find applications in the very near future in different industrial. Further screenings are underway as well as research into understanding the structure-function relationships of these unusual polymers.