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In this work, the phase behavior of the poly(vinyl alcohol) (PVA)/alkyl ethoxysulfate (AES)/water ternary system is investigated at 25 °C. The PVA/AES/water ternary phase diagram is conducted which shows that there are two main phases corresponding to the solid phase and the hexagonal liquid crystalline phase (H) in the ternary system. Besides these two phases, a high-viscosity liquid phase (L2) and a micellar phase (L1) can also be found in the phase diagram, although they just occupy small areas. Polarizing optical microscopy and small-