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Electrokinetic demixing of aqueous two‐phase polymer/salt systems is demonstrated, resulting in significant enhancement in demixing rates by about 1–4‐fold. The effect of field polarity, field strength, volume ratio, and phase composition on phase demixing has been studied. Further the influence of these parameters on phase demixing could be explained based on the hydrodynamic flow‐electroosmotic flow (HEF) model.