Currently, efforts are being made to utilize more natural biological systems as alternatives as a way to replace fossil forms of carbon. There is a growing concern at global level to have nontoxic, nonhazardous surface-active agents; contrary to synthetic surfactants, their biological counterparts or biosurfactants play a primary function, facilitating microbial presence in environments dominated by hydrophilic-hydrophobic interfaces. Algal and microbial biosurfactants/bioemulsifiers from marine and deep-sea environments are attracting major interest due to their structural and functional diversity as molecules actives of surface and an alternative biomass to replace fossil forms of carbon. Algal and microbial surfactants are lipid in nature and classified as glycolipids, phospholipids, lipopeptides, natural lipids, fatty acids, and lipopolysaccharides. These metabolic bioactive products are applicable in a number of industries and processes, viz., food processing, pharmacology, and bioremediation of oil-polluted environments. This chapter presents an update of the progress and potentialities of the principal producers of exopolysaccharide (EPS)-type biosurfactants and bioemulsifiers, viz., macro- and microalgae (cyanobacteria and diatoms) and bacteria from marine and extreme environments. Particular interest is centered into new sources and applications, viz., marine and deep-sea environments and promissory uses of these EPSs as biosurfactants/emulsifiers and other polymeric roles. The enormous benefits of these molecules encourage their discovery, exploitation, and development of new microbial EPSs that could possess novel industrial importance and corresponding innovations.