Electrokinetic demixing is attempted for faster separation of aqueous two-phase systems. Electrokinetic demixing is carried out employing the PEG/potassium phosphate phase system for the separation of biomolecules like Bovine serum albumin and C-phycocyanin. The effect of field polarity, field strength, and concentration of proteins on partitioning are studied at two different tie lines. In spite of the application of the electric field, BSA as well as C-phycocyanin partitioned to their preferred phases. Demixing time decreased by 50% at 4.4V/cm when compared to gravity. Electrokinetic demixing could decrease the phase demixing time without affecting the partitioning of the target protein.