In this work, two‐phase electrophoresis as a more highly effective back‐extraction method was studied. With 33% TOA in n‐hexanol as organic solvent, citric acid and succinic acid can be back‐extracted to the aqueous phase by two‐phase electrophoresis. Compared with the traditional back‐extraction ways, there is no phase mixing, phase separation, or other chemicals requirement. So, the process can be called an environmentally friendly process. Some influence factors, such as the distance between the electrode to the interface, time, initial concentration, and electric current density, are discussed. Our experimental results show that the distance from the upper electrode to the interface has little influence on the mass transfer performance. Hence, it is better to keep the distance as low as possible, but the interface cannot be destroyed. The overall mass transfer quantity increases but the electric current efficiency decreases with an increase in the time. A higher electric current density gives better mass transfer performance. With the initial concentration increasing, both the overall mass transfer quantity and electric current efficiency increase. For the acids with lower distribution coefficient at normal conditions, a much higher back‐extraction ratio can be reached.