Aqueous two-phase systems of cetyltrimethylammonium bromide and sodium dodecyl sulfate mixtures without and with polyethylene glycol (PEG) added have been studied at 313.15 K. The results have shown that PEG has a strong effect on the phase diagram of ATPS and microstructures of surfactants aggregates. The addition of PEG leads to the formation of bigger surfactant aggregates, which can be attributed to both the screening effect and the connection
effect of PEG. All ATPS, especially those with PEG added, may have potential applications in separation and purification of biomaterials.