Microbial biosurfactants are amphipathic molecules having typical molecular weights of 500-1500 Da, made up of peptides, saccharides or lipids or their combinations. In biodegradation processes they mediate solubilisation, mobilization and/or accession of hydrophobic substrates to microbes. They may be located on the cell surface or be secreted into the extracellular medium and they facilitate uptake of hydrophobic molecules through direct cellular contact with hydrophobic solids or droplets or through micellarisation. They are also involved in cell physiological processes such as biofilm formation and detachment, and in diverse biofilm associated processes such as wastewater treatment and microbial pathogenesis. The protection of contaminants in biosurfactants micelles may also inhibit uptake of contaminants by microbes. In bioremediation processes biosurfactants may facilitate release of contaminants from soil, but soils also tend to bind surfactants strongly which makes their role in contaminant desorption more complex. A greater understanding of the underlying roles played by biosurfactants in microbial physiology and in biodegradative processes is developing through advances in cell and molecular biology.