A process for isolating rhamnolipids is provided. The process includes providing an aqueous medium containing at least one rhamnolipid and having a pH of less than 6. Next, the aqueous medium is brought into contact with at least one organic solvent to provide a multiphase system and then the aqueous phase is separated off. The pH is then increased to a value of 6 or more to provide a multiphase organic system. Next, a rhamnolipid-enriched organic phase is separated off. An optional step of further purifying the rhamnolipid may be performed.