This Review highlights the potential of new electromigration-based sample pretreatment techniques for bioanalysis. Sample pretreatment is a challenging part of the analytical workflow, especially in the fields of peptidomics and metabolomics, where the analytes are very diverse, both in physicochemical properties and in endogenous concentration. Electromigration-based techniques have several strengths, such as fast selective analyte concentration and that complementary information on the content of a sample can be obtained when compared with more conventional (chromatography-based) techniques. In the past decade, various new electromigration-based sample pretreatment techniques have been developed, and importantly, new instrumental setups. In this Review, we provide an introduction on electromigration and its strengths. Then, selected examples of electromigration-based sample pretreatment techniques and instrumentation are discussed, namely free-flow electrophoresis, isoelectric focusing, isotachophoresis, electrodialysis, electromembrane extraction and electroextraction. Finally, the promising perspectives of electromigration-based sample pretreatment techniques are outlined.