The recent societal requirements to explore more environmentaly friendly solutions in the field of sample preparation have gained increasing focus during recent years. A reduction in the consumption of hazardous organic solvent owing to environmental and cost perspectives, small amounts of sample available and time reduction, have been major incentives for scientists to miniaturize existing sample preparation methods. Some of these challenges were addressed by the introduction of electromembrane extraction (EME), a totally new extraction principle where a potential difference is applied across a thin organic membrane immobilized in the pores in the wall of a porous polypropylene membrane. The potential difference is utilized to extract charged analytes of interest from the sample, across the organic membrane, and into an aqueous acceptor solution present inside the lumen of the hollow fiber. This article focuses on the potential of EME in bioanalysis, including discussions of EME performance.