A new technique of two-phase electro-electrodialysis process has been developed and applied to separate acetic acid from its solution. Normally an aqueous phase is applied as the anolyte solution in a normal electroelectrodialysis process. In the new technique an emulsion composed of 49.9% kerosene, 49.9% water, and 0.2% Tween was used as the anolyte instead of the aqueous phase. The influences of the electrical current and the initial anolyte and catholyte concentration on the performance of the normal or the new process have been studied. The experimental results showed that the new technique could control the electroosmosis and osmosis effectively. Almost no anolyte volume change has been observed during the two-phase electro-electrodialysis process. And also much higher concentrated ratio with almost 100% recovery can be reached with the new technique. In the process, the electrical current efficiency was kept around 50%. Furthermore it was found that the concentration difference between the anolyte and the catholyte has less influence in the two-phase electro-electrodialysis process than that in the normal electrodialysis process.