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The environment pollution with hydrophobic hydrocarbons is a serious problem that requires development of efficient strategies that would lead to bioremediation of contaminated areas. One of the common methods used for enhancement of biodegradation of pollutants is the addition of biosurfactants. Several mechanisms have been postulated as responsible for hydrocarbons bioavailability enhancement with biosurfactants. They include solubilization and desorption of pollutants as well as modification of bacteria cell surface properties. The presented review contains a wide discussion of these mechanisms in the context of alteration of bioremediation efficiency with biosurfactants. It brings new light to such a complex and important issue.