DOI: 10.1002/elps.201800203 An on-line, single step electroextraction is demonstrated for capillary electrophoresis and microchip electrophoresis. The electroextraction employed an aqueous two-phase system (ATPS) formed by one 500 kDa dextran-rich phase added to the samples and a second 6 kDa poly(ethylene glycol)-rich phase containing 5.0 mol/L acetic acid. The second phase acted as background electrolyte. The ATPS enabled electrically driven extraction of target compounds, while demonstrated to retain sodium ions. The ATPS electrodriven system was applied on the determination of glutamate in soy sauces samples.